The Scientific Method Classification of matter Classification of matter Chemistry: basic definitions

• Matter is made of atoms.  Matter: anything that occupies space and has mass, anything made up of atoms.
Any matter that can be identified as a particular “type” is called a “substance”
• 114 elements.
 Physical Properties: characteristics observed without changing basic identity of No bonds between atoms
• About 90% available from natural sources substance. The key is that molecular structure of substance is not altered. are formed or broken
Note the feedback loops. e.g. colour, melting point, density
Sometimes new information does • Compounds are comprised of two or more elements.
not agree with a theory, means we  Chemical Properties: any characteristic of a substance that involves ability (or
must change or modify a theory. • Molecules are the smallest units of compounds. inability) of substance to react to form other substances. The molecular structure
of substance being studied (reactant) is altered if reaction occurs. New bonds between
This is not a failure of science, but e.g. flammability of carbon in oxygen gas atoms are formed
demonstrates the correct way that
H
O He
e.g. non reactivity of Au in hydrochloric acid solution and/or broken
science advances over time. H
Figure 1-1 The Scientific Method Illustrated  Intensive Properties: characteristic not depending on amount of substance
present. They depend on the internal makeup of the substance.
e.g. density, temperature, boiling point of a pure substance
Emphasis on science through “hypotheses that can be tested”
- Important in current discussions of “Evidence-based policy” and even “Fake news” Figure 1-4 A classification scheme for matter
 Extensive Properties: characteristics depending on amount of substance present
For more, check out the TED talk on this by Prof. Naomi Oreskes (link in onQ) 3 7 5 e.g. mass, volume, heat content 4

The Mole Concept: (text Section 2.7) - important “unit” in chemistry!

•Homogeneous: a substance composed of one phase and uniform in composition and properties throughout, Measurements of matter: SI Units Precision and Accuracy
until reaching the dimensions of molecules (nanometers)
 atoms and molecules are extremely small, numbers are awkwardly large
 Precision refers to how closely individual experimental readings agree with one another.
Left balance has low precision, right balance has high precision.
 Accuracy refers to how closely experimental readings agree with the true values.  measurable amounts expressed as moles of atoms or molecules, also defined as
Do these two measurements agree? Is one balance more likely to be accurate? Avogadro’s number of particles (NA)

 until recently, a mole (abbreviation mol) was defined as the number of elementary particles
(atoms) found in 12 g of 12C
“Pure” salts of copper Copper solutions

 new definition from IUPAC in 2018: NA is exactly 6.02214076 × 1023 elementary entities

Heterogeneous: a substance containing two or more distinct phases.  We will work with NA = 6.022 × 1023 mol-1
Composition and physical properties vary from one part of mixture
to another. Note: this number is huge
(grains of sand on Earth = 7.5 × 1018)

Copyright © 2017 Pearson Canada Inc.

Milk is a heterogeneous mixture. low precision high precision

6 9 3 5

Mole Relationships –“the hub” – this brings the mole-based calculations together
Molar mass (M): (Text Section 2.8) Mole concept used for gases: (text Section 6.2, 6.3) - should also be reviewed, Mole, mass, volume and number of particles related as follows.
we’ll return to the rest of Ch. 6 soon…
Balance each of the following equations  mass of one mole (Avogadro’s number) of atoms, molecules or other particles
1. Choose this to have coeff 1
2. That makes this 4  units of molar mass: grams per mole (g/mol or g·mol-1)
3. and makes this 3 Mass Meaning of symbols
4. Clean up by making this 12 Molar volume: Gas Volume
Al4C3 + 12 H2O 3 CH4 + Practice Problem #2
Symbol m  R is the ideal gas constant equal to:
4 Al(OH)3  Volume occupied by 1 mol of a substance Symbol V
(g)
Find the molar mass of sodium sulfite Na2SO3 (L) 8.3145 _L·kPa_ = 0.082058 _L·atm_
 Units are L or m3 (1 m3 = 1000 L)
mol·K mol·K
1. Choose this to have coeff 1
 Most common for gases (could use for solids or liquids, but much smaller as their densities  P is gas pressure measured in kilopascals or
2. That makes this 3
3. Balance PO4 as group, gives this a 2 Na 22.98976928 x 2 = 45.97953856 are much higher – could express in cm3) PV = nRT
Number of
n = m/M
atmospheres (kPa or atm)
4. clean-up with 3 Moles  V is gas volume measured in litres (L)
3 MgO + 2 H3PO4 Mg3(PO4)2 + 3 H2O S 32.06 x 1 = 32.06  Standard Temperature and Pressure (STP) defined as 273.15 K (0 ⁰C) and 100.000 kPa. Symbol n  T is gas temperature in Kelvins (K) 0 °C = 273.15 K
Molar volume gas = 22.711 L at STP (mol)  n is the number of moles (mol)
1. Choose this to have coeff 1 n = # particles/NA C = n/V
2. This must also be 1  m is the mass in grams (g)
3. and makes this 2 O 15.999 x 3 = 47.997  M is molar mass in grams per mole (g·mol-1)
4. 2 H2O on other side makes this 4  Standard Temperature and Pressure (STP) were defined in some sources as 273.15 K (0 ⁰C)
5. Cleanup makes this 1
 NA is Avogadro’s number (mol-1)
and 101.326 kPa (1.000 atm), but IUPAC recommends no longer using these for STP. Number of Atoms Concentration of a
MnO2 + 4 HCl MnCl2 + 2 H2O + Cl2 Molar mass = 126.04 g/mol or Molecules Solution Symbol C  C is concentration in moles/litre (mol·L-1)
Molar volume = 22.414 L at these values =nsolute/Vsolution  nsolute is the moles of solute (mol)
(mol/L)  Vsolution is the volume of solution (L)

The molecular formula numbers 1, 2 and 3 are “exact numbers”. How many significant figures do they have?
3 6 7 Note: volume of pure solids and liquids (made of one element or compound) comes from mass and density 8

Sample problem quiz #1 Sample problem quiz #2 PV = nRT Balanced equations – reaction “stoichiometry”
Balancing and Using Chemical Equations
What is the volume (mL) of 1.000 kg of liquid mercury? (Density = 13.5 g/cm3) Calculate the mass (g) of 1.00 L of oxygen gas (O2) at 273 ⁰C and 202 kPa. • During a chemical reaction, atoms in reacting materials (reactants)
 R for P in kPa = 8.3145 kPa·L/mol·K are rearranged to produce different substances (products).
 Gives us mole relationships that exist between reactants and products (stoichiometry)
Multiple unit conversions needed. Have mass in kg but density has g units, so need to convert.
Need to get from vol (L) to mass (g), from “hub” we can 0 ⁰C = 273.15 K
g start with vol and get to mol, then go from mol to g  Typical problems - check and balance chemical reactions
1.000 kg x 1000 = 1000 g (we have 4 sig figs here…) 3
kg Rearrange PV = nRT to calculate n 1 1
1
 See “Review balancing equations” practice exercise on onQ 2 2
Now with mass in g, can use density to convert to cm3 PV  Conservation of atoms on left (reactants) and right (products) sides of equation 3 2
n= Note: 273 ⁰C + 273.15 gives T = 546.15 K 1
RT 2
1000 g The “.15” digits are not significant, but kept React to
= 74.07407 cm3 (writing all the digits from Excel for emphasis) Previous slide: O2 + 2H2 2H2O
g 202 kPa x 1.00 L in this intermediate calculation so the reactants produce products
13.5 n= = 0.044484 mol answer agrees with that on a spreadsheet
cm3 kPa∙L
8.3145 x 546.15 K or calculator
It’s trivial in this example, but final units need to be mL rather than cm3 mol∙K Another example: “balance this reaction” KClO3(s) KCl(s) + O2 (g)
1O2 + 2H2 2H2O
mL
74.07407 cm3 x 1 = 74.07407 mL (how many sig figs in the “1” mL/cm3?) To go from mol to g, we need molar mass [Link] O2 = 31.998 g/mol Gives the answer: 2 KClO3(s) 2 KCl(s) + 3 O2 (g)
cm3
potassium potassium oxygen Notice that no atoms are lost in the reaction but simply rearranged.
Finally, only multiplication-division used, so number of sig figs is same as factor with fewest (13.5) Mass: 0.044484 mol x 31.998 g/mol = 1.423397 g
chlorate chloride Chemical bonds are broken and new chemical bonds are formed.
74.07407 mL  74.1 mL Analysis gives 3 sig figs so: Mass of 1.00 L O2 is 1.42 g 3 All atoms must be accounted for. 2
 Example #2 Calcium oxide reacts with hydrochloric acid to produce calcium chloride and water. If 60.4 g of
Real chemical reactions and “stoichiometric” amounts calcium oxide and 69.0 g of hydrochloric acid are added, a reaction proceeds until one of the reactants runs out.
Balanced equations – reaction “stoichiometry” Balanced equations – reaction “stoichiometry” What mass of calcium chloride is formed?
• Real reactions normally don’t use exact stoichiometric amounts of all reactants CaO (s) + 2 HCl (aq) H2O (l) + CaCl2 (aq)
• The reaction proceeds until one of the reactants runs out Example # 1
 Do we ever have fractions as coefficients in balanced equations? Potassium chlorate when heated decomposes to produce potassium chloride and oxygen
- we call this the limiting reagent (or limiting reactant) 1
gas. Calculate mass of potassium chlorate needed to produce 75.0 L of oxygen gas at STP. Enough to react Enough to react mol CaCl2 = mol HCl
 Yes! But for this class only if it’s a “defined” type of equation - other reactants are in excess O2 + 2H2 2H2O with 2.16 mol HCl with 0.946 mol CaO
2
• e.g. combustion reactions, “formation” reactions, reduction/oxidation reactions 2 KClO3(s) 2 KCl(s) + 3 O2 (g) 1
CaO is in excess HCl is limiting = 2 1.89 = 0.946
- have a central molecule that usually gets a coefficient of 1 In excess = 1.08 mol = 1.89 mol = 0.946 mol
= 2.20 mol = 3.30 mol 100.0·75.0
n=
• Example: combustion of methanol 8.314·273.15
Molar Mass n = 3.30 mol
3 = 122.54 g/mol From balanced equation:
CH3OH + 2 O2 CO2 + 2H2O 2 mol KClO3 per 3 mol O2
In excess
or 2 mol KClO3 / 3 mol O2 P·V
n=
Draw with excess R·T Molar Mass
or 2 mol KClO3 Molar Mass Molar Mass
= 105.01 g/mol
• Example: “formation” of ammonia molecules on reactant 2.20 mol x 122.54 g/mol
3 mol O2
x 3.30 mol O2 = 56.077 g/mol = 36.46 g/mol
and product sides, = 270 g
3 1 since they are still = 2.70 x 102 g 60.4 g 69.0 g = 105 g
2 H2 + 2 N2 NH3 there at end
= 2.20 mol KClO3

4 5 3
Will form 1.05x102 g CaCl2 6
(theoretical yield)

Percent Yield Balancing simple chemical reaction equations by inspection

CaO (s) + 2 HCl (aq) H2O (l) + CaCl2 (aq) Balanced equations – reaction “stoichiometry”
Example #3 Balance each of the following equations
In the previous example, the theoretical yield of calcium chloride produced turned out to A “balanced equation” 1. Choose this to have coeff 1

 has equal number of each type of atom on both sides of the equation
2. That makes this 4
Gives us mole relationships that exist between reactants and products (stoichiometry)
be 105 g. Suppose that 78 g was produced as the measured product mass after doing 4. Clean up by making this 12
3. and makes this 3

this reaction in the lab. Find the percent yield.  represents the initial and final states of the process
Al4C3 + 12 H2O 3 CH4 + 4 Al(OH)3 Typical problems - check and balance chemical reactions
 usually does not represent the actual chemical process involved but is the total of all elementary steps
(reaction mechanism to be studied in Winter term)
Actual yield
Percent yield = x 100  used to establish quantitative relationships among reactants and products of a reaction. This is known See “Review balancing equations” practice exercise on onQ
Theoretical yield as reaction stoichiometry. 2. That makes this 3
1. Choose this to have coeff 1

3. Balance PO4 as group, gives this a 2 Conservation of atoms on left (reactants) and right (products) sides of equation
4. clean-up with 3
3 MgO + 2 H3PO4 Mg3(PO4)2 + 3 H2O
78
To balance simple equations, can often do by “inspection”:
Previous slide: O2 + 2H2 2H2O
x 100 = 74%
105 1. Choose this to have coeff 1
2. This must also be 1
• Balance elements that occur in only one compound on each side first. 3. and makes this 2
• Balance free elements last (includes elemental forms: O2, H2, Cl2, etc.). 4. 2 H2O on other side makes this 4 5. Cleanup makes this 1 Another example: “balance this reaction” KClO3 (s) KCl(s) + O2 (g)
• Balance unchanged polyatomics (or other groups of atoms) as groups. MnO2 + 4 HCl MnCl2 + 2 H2O + Cl2
• Fractional coefficients can be used, but are normally cleared at the end by multiplication to simplify Gives the answer: 2 KClO3 (s) 2 KCl(s) + 3 O2 (g)
the final form.
- if the reaction is a standard form referring to a specific molecule, fractional coefficients might be kept on potassium potassium oxygen
other reactants and products to give the specific molecule a coefficient of 1. chlorate chloride
7 1 3 3

Example #2 Calcium oxide reacts with hydrochloric acid to produce calcium chloride and water. If 60.4 g of
Balancing simple chemical reaction equations by inspection calcium oxide and 69.0 g of hydrochloric acid are added, a reaction proceeds until one of the reactants runs out.
Balanced equations – reaction “stoichiometry” Balanced equations – reaction “stoichiometry” What mass of calcium chloride is formed?
CaO (s) + 2 HCl (aq) H2O (l) + CaCl2 (aq)
A “balanced equation” Example # 1
Do we ever have fractions as coefficients in balanced equations? has equal number of each type of atom on both sides of the equation Potassium chlorate when heated decomposes to produce potassium chloride and oxygen
represents the initial and final states of the process 1
gas. Calculate mass of potassium chlorate needed to produce 75.0 L of oxygen gas at STP. Enough to react Enough to react mol CaCl2 = mol HCl
Yes! But for this class only if it’s a “defined” type of equation usually does not represent the actual chemical process involved but is the total of all elementary steps 2
with 2.16 mol HCl with 0.946 mol CaO
2 KClO3 (s) 2 KCl(s) + 3 O2 (g) 1
• e.g. combustion reactions, “formation” reactions, reduction/oxidation reactions (reaction mechanism to be studied in Winter term) CaO is in excess HCl is limiting = 2 1.89 = 0.946
- have a central molecule that usually gets a coefficient of 1 used to establish quantitative relationships among reactants and products of a reaction. This is known
as reaction stoichiometry. = 1.08 mol = 1.89 mol = 0.946 mol
= 2.20 mol = 3.30 mol 100.0·75.0
n=
• Example: combustion of methanol 8.314·273.15
Molar Mass n = 3.30 mol
To balance simple equations, can often do by “inspection”: From balanced equation:
3 = 122.54 g/mol
CH3OH + 2 O2 CO2 + 2H2O • Balance elements that occur in only one compound on each side first. 2 mol KClO3 per 3 mol O2
or 2 mol KClO3 / 3 mol O2 P·V
• Balance free elements last (includes elemental forms: O2, H2, Cl2, etc.). n=
R·T Molar Mass
or 2 mol KClO3 Molar Mass Molar Mass = 105.01 g/mol
• Example: “formation” of ammonia • Balance unchanged polyatomics (or other groups of atoms) as groups. 2.20 mol x 122.54 g/mol x 3.30 mol O2
3 mol O2 = 56.077 g/mol = 36.46 g/mol
• Fractional coefficients can be used, but are normally cleared at the end by multiplication to simplify = 270 g
3 1 the final form. = 2.70 x 102 g = 2.20 mol KClO3 60.4 g 69.0 g = 105 g
2 H2 + 2 N2 NH3 - if the reaction is a standard form referring to a specific molecule, fractional coefficients might be maintained
to give the specific molecule a coefficient of 1.
4 7 11
Will form 1.05x102 g CaCl2 15
(theoretical yield)

Theoretical yield and percent yield • How many grams of chlorine are needed to react with A mixture of 3652 grams of carbon dioxide and 2555 grams of
Example 0.245 grams of hydrogen to give hydrogen chloride? ammonia react to give (NH2)2CO and water.
Examples using previous balanced equation
• How much hydrogen chloride is formed? How much (NH2)2CO is formed?
• A certain synthetic process yields
CaO(s) + 2HCl(aq) H2O(l) + CaCl2(aq)
7.83×10-2 g of product per second. After 5.00 days of Balance the equation: H2 + Cl2 ¾¾® 2 HCl
continuous reacting, how many kilograms will be We know that all the hydrogen is used up based on the wording in the question. Balance the equation: 2NH3 + CO2 ¾¾® (NH2)2CO + H2O
In the case with 1 mole of CaO and 3 moles of HCl (CaO is limiting), produced? So start with the amount of hydrogen First, determine what is used up. We make a guess at ammonia and see
the theoretical yield of CaCl2 is 1 mole how much CO2 we need.
0.245 g H2 1 mol H2 1 Cl2 70.906 g
- the expected amount if the reaction goes to completion, according to the stoichiometry = 8.67 g Cl2 2555 g NH3 1 mol NH3 1 CO2 44.01 g CO2
2.016 g H2 1 H2 1 mol = 3301 g CO2
17.034 g NH3 2 NH3 1 mol CO2
Suppose after doing this reaction, 0.87 moles of CaCl2 are produced (the actual yield).
The percent yield is: We know that all the hydrogen is used up based on the wording in the question. Since we have more than enough CO2, we guessed correctly.
So start with the amount of hydrogen Ammonia is the limiting reagent.
Actual yield 2555 g NH3 1 mol NH3 1 (NH2)2CO 60.061 g (NH2)2CO
Percent yield = x 100 0.87 0.245 g H2 1 mol H2 2 HCl 36.46 g
Theoretical yield = x 100 = 87% = 8.86 g Cl2
1.00 17.034 g NH3 2 NH3 1 mol (NH2)2CO
2.016 g H2 1 H2 1 mol

See balancing equation exercise and stoichiometry-based word problem on onQ

16 = 4504 g (NH2)2CO
Nomenclature: • Avoid needing to memorize separate common names
Molecular structure and naming molecules Simple compounds (inorganic) Simple compounds
for all compounds
Scheme for • Names are derived from the structure/composition • Can use oxidation states or valence shell electrons to determine • We use the oxidation state to keep track of the number of electrons
• Generally divide into Organic and Inorganic
systematic compounds à Means the structure can be derived from the systematic name! structure from composition that have been gained or lost by an element.
naming of • A compound must be neutral (equal number of electrons gained and
organic and Organic Compound
Valence Shell Electrons: lost) à link with compound structure and composition
• A molecule containing carbon and hydrogen atoms
inorganic • are available for bonding with other atoms
• May have additional elements, especially oxygen and
compounds nitrogen • can be determined from position in the Periodic Table
• also known from the oxidation states of the elements
Inorganic Compound • linked to electron affinities of atoms and Lewis structure of compounds Metals Non-metals
• Any molecule that doesn’t match the rules for organic àmore later tend to lose electrons tend to gain electrons
compounds!
Na → Na+ + e– Cl + e– → Cl–
• Always exceptions: e.g. H2CO3 (carbonic acid) is an
inorganic compound
Figure 3-1: Several representations of the compound acetic acid

Write the chemical formula for:

Binary Compounds: No Net Charge Example: metal and non-metal a) potassium chloride KCl
________________________________

Formed from two For a binary compound with one metal and one non-metal: b) sodium oxide Na2O
________________________________
• Charges must balance in overall formula
• Metallic element is named first • sodium chloride NaCl
elements only • Use “expected” charges from oxidation state, valence electrons, etc… to determine subscripts in c) aluminum fluoride AlF3
________________________________
• Non-metallic element named with ending changed to “-ide” structure to balance charges • sodium oxide Na2O
*d) copper oxide copper has more than one
________________________________ oxidation state
• Positive ion (cation) written before negative ion (anion) • calcium chloride CaCl2
• If metal and non- • Since subscripts can be easily determined from expected charges, name does not contain *e) iron chloride iron has more than one oxidation
________________________________ state
metal, will be an information about the subscripts or molecular formula!
ionic compound Write the name of the following formulae:
Expected oxidation state Expected oxidation state f) CaO calcium oxide
________________________________
• If two non-metals, +1 +2 +3
+4
or -3 -2 -1 0 (noble) +1 +2 +3
+4
or -3 -2 -1 0 (noble) g) BaI2 barium iodide
________________________________
will be a covalent -4 -4
h) Rb2O rubidium oxide
________________________________
compound H sometimes
can be -1
H sometimes
can be -1
can’t call both of these “mercury oxide”
*i) Hg2O ________________________________
-need a modified approach
*j) HgO ________________________________

Notice that d) and e) and i) and j) present some problems.

What about elements with more than one common oxidation state?? Non-IUPAC system: -ous, -ic Symbol Systematic Common Symbol Systematic Common
Example: Non-IUPAC naming Note that we have Cu+ and O2-
IUPAC SYSTEM Cu can be Cu+ or Cu2+
IUPAC System Name Name Name Name
cuprous oxide
• If two potential oxidation states: Cu+ copper (I) cuprous Hg22+ mercury (I) mercurous Cu2O ________________________
Cu+ = cuprous
A àInternational Union
naming system called the of Puresystem
IUPAC and Applied Chemistry
(International Union of Pure and Applied
• Lower oxidation form ending “-ous”
Chemistry) was developed to eliminate such difficulties. Cu2+ copper (II) cupric Hg2+ mercury(II) mercuric
• Higher oxidation form ending “-ic” PbS2
If you are naming a chemical compound from a formula, and the first element in the formula has
Fe2+ iron (II) ferrous Pb2+ lead (II) plumbous Plumbic sulfide ________________________
Pb can be Pb2+ (ous) or Pb4+ (ic)
If the
more thanfirst elementnumber,
one oxidation in thethe formula
oxidationhas more
number than
for this one oxidation
multi-valent element isnumber,
placed as • Must also know Latin names of elements… Fe3+ iron (III) ferric Pb4+ lead(IV) plumbic
the oxidation
a Roman number
Numeral, in brackets, for
afterthis
namemulti-valent
of the [Link] is placed as a
Sn2+ tin (II) stannous Co2+ cobalt(II) cobaltous
FeCl2 ferrous chloride
________________________
Fe can be Fe 2+ (ous) or Fe3+ (ic)
Roman Numeral, in brackets, after the name of the element.
This method can be used to name any compound. Sn4+ tin (IV) stannic Co3+ cobalt(III) cobaltic
copper = cuprum iron = ferrum
Cu2O Cr2+ chromium (II) chromous Au+ gold(I) aurous
copper (I) oxide is __________________ lead = plumbum tin = stannum Stannous nitride Sn3N2 Sn can be
________________________ Sn2+ (ous) or Sn4+ (ic)
Cr3+ chromium(III) chromic Au3+ gold(III) auric
Hg3N is mercury(I) nitride
__________________
Mn2+ manganese(II) manganous
FeCl2 is iron(II) chloride
__________________ Mn3+ manganese(III) manganic

iron (III) sulfide is Fe2S3

__________________

Compounds with Polyatomic Ions:

Binary Compounds: For a binary compound with two non-metals: Polyatomic IonsIons:
Compounds with Polyatomic Polyatomic Anions
Not all compounds are binary. This can easily be noticed by flipping through a chemistry book
and noting the names of many compounds not ending in 'ide'.
Formed from two • Must state number of each element explicitly in the name
•Not
Notall compounds are binary. This can easily be noticed by flipping through a chemistry book
all compounds are binary!! The Polyatomic
•Compounds ions in those acids are anions
not binary, generally contain a polyatomic ion consisting of a number of atoms which
elements only • Use prefixes to indicate formula numbers and noting the names of many compounds not ending in 'ide'.

• Written from left-most element to right Thearound

•hang oxidation number
as a group. of the
The group anion
remains is equal
unchanged toathe
during number
chemical ofand
reaction, H found
has a
Compounds not binary, generally contain a polyatomic ion consisting of a number of atoms which single oxidation number.
• First element named remains unchanged Canaround
•hang containas a a polyatomic
group. The group ion
remains unchanged during a chemical reaction, and has a in the acid
• If metal and non- • Second element ending changed to “ide” single oxidation number. Key•toRemember,
rememberingoxidation number for
many of polyatomic ionsH isis knowing
1+ the five oxy-acids listed below (and
• an ion that comprises of a group of atoms
metal, will be an several others which will be shown to you). They will unlock thousands of chemical formulae
ionic compound
• “mono” dropped from left-hand element the
Key• to group is unchanged
remembering during aions
many of polyatomic chemical reaction
is knowing the five oxy-acids listed below (and •toLink
you. “ic” in name of acid to “ate” in name of ion
• theothers
several groupwhich
has awill
single oxidation
be shown number
to you). They will unlock thousands of chemical formulae
Prefixes to you. OXY-ACIDS
• If two non-metals, chlorate
HIO3, ion
will be a covalent mono 1 hexa 6 Examples of compounds with a polyatomic ion:
•OXY-ACIDS chloric acid HClO3 ClO31- (iodic bromic HBrO3)
nitric acid HNO3 NO31- nitrate ion
di 2 hepta 7
(or molecular) chloric acid HClO3 (iodic HIO3, bromic HBrO3) sulphuric acid H2SO4 SO42- sulfate
(selenic H2ion
SeO4, telluric H2TeO4)
tri 3 octa 8
compound tetra 4 nona 9
nitric acid HNO3 carbonic acid H2CO3 CO32- carbonate ion
sulphuric acid H2SO4 (selenic H2SeO4, telluric H2TeO4) phosphoric acid H3PO4 PO43- phosphate ion
penta 5 deca 10 carbonic acid H2CO3
phosphoric acid H3PO4
 Name the Polyatomic Ion Exercise: Name The Acid Isomers Examples
• Constitutional isomers (or structural isomers) have the same molecular
formula but a different connection scheme for the atoms Draw a structural formula for the following
Hypo_ite Ite ate Per____ate Hypo_ous Acid ous Acid ic Acid Per____ic Acid
1) 3,5-diethyloctane
Structural formula “hybrid” heptane or n-heptane
ClO- ClO2- ClO3- ClO4- HClO HClO2 HClO3 HClO4 structural-condensed formula Line-angle formulas or line structures

___ NO2- NO3- ___ ___ HNO2 HNO3 ___

___ SO3-2 SO4-2 ___ ___ H2SO3 H2SO4 ___ 2) 3-ethyl-2-methylpentane

___ H2CO2 H2CO3 ___
___ CO2-2 CO3-2 ___ n-pentane 2-methylbutane 2,2-dimethylpropane
___ H3PO3 H3PO4 ___ 2-methylbutane or methylbutane (only 2 is possible)
___ PO3-3 PO4-3 ___
Isomers of butane, C4H10 Isomers of pentane, C5H12
<–––––––– Subtract an O Add an O ––––––––> 3) 2,2,5,6-tetramethylheptane
<–––––––– Subtract an O Add an O ––––––––>
Why not write “2-methylpropane”?
Can see examples of primary (1o), secondary
(2o), tertiary (3o) and quaternary (4o)carbons 2,2,4-trimethylpentane

Halides as functional groups Functional groups define the type of compound Functional groups define the type of compound Functional groups define the type of compound
• Need to be familiar with all the groups in this table • More Table 26.2: Need to be familiar with all the groups in this table • More Table 26.2: Need to be familiar with all the groups in this table
• Halides named as substituents (fluoro-, chloro-, bromo-, iodo-)
• Chain number rules similar to adding methyl
• Unique functional group: molecule still called an “alkane”

Note: strict IUPAC name would be “Hexan-3-one” but “3-Hexanone” is a very common alternate.
We will accept both versions in this course.

Review: nomenclature rules for alkanes and substituted alkanes

Functional groups define the type of compound
• More Table 26.2: Need to be familiar with all the groups in this table
Branched branches Examples
1) Select the longest continuous carbon chain. • What do you do when there are
2) Every branch is considered an alkyl group. branches on branches? Draw a structural formula for the following
3) Number the base chain so substituents appear at the lowest 1. Identify the longest part of the 1) 3,5-diethyloctane
numbers possible . branch and use it as a base name heptane or n-heptane
with ending “ –yl”
4) Name each substituent according to its identity, use di, tri,
2. Number carbons on the branch
tetra, and so on.
starting with the carbon attached to 2) 3-ethyl-2-methylpentane
5) Separate numbers with commas but no spaces and numbers the main (longest) chain
from letters with hyphens. 3. Identify and number each branch
6) List substituents alphabetically, prefixes are ignored. off the branch, again with name of 2-methylbutane or methylbutane (only 2 is possible)
each branch off branch ending in “ –
yl” 3) 2,2,5,6-tetramethylheptane
2,2,4-trimethylpentane, 4. Name entire branch and attach to
an isomer of octane the name of the main chain in the
molecule 2,2,4-trimethylpentane

Alkanes and conformations Showing conformation through Newman Projections Showing conformation through Newman Projections Free rotation around single bonds
These are both conformers of 4-methylheptane.
Simple rotation around carbon #4 switches from one to the other
CH3
ˡ
CH2 1
ˡ 2 1 2
CH2 CH3
ˡ
CH3-CH2-CH2-CH-CH ˡ
CH3-CH2-CH2-CH-CH
3 2-CH2-CH3

• Saturated hydrocarbons: Only single bonds. C1

• Normal formula is CnH2n+2 C1 The dihedral angle, θ, refers
• “Free” rotation around C-C single bonds, have multiple conformations to the angle of rotation
• Molecules change between conformations by simple bond rotations about a carbon-carbon bond.
• physical change, not a chemical change
• different conformations are same molecule, same properties
• conformations are NOT isomers
• FIGURE 26-6 Staggered and eclipsed conformations of ethane
2 3 4 5
Newman Projections for Butane Newman Projections for Butane Cycloalkanes Alkenes and Alkynes
Alkanes Cycloalkanes Alkanes Alkenes Alkynes
• Saturated hydrocarbons: Only single bonds. • Saturated hydrocarbons: Only single bonds. • Saturated hydrocarbons: Only • Unsaturated hydrocarbons: • Unsaturated hydrocarbons:
• Normal formula is CnH2n+2 • Normal formula is CnH2n single bonds. contains double bond contains triple bond
• “Free” rotation around C-C bonds, have multiple • Constrained rotation around C-C bonds, have • Normal formula is CnH2n+2 • Normal formula is CnH2n • Normal formula is CnH2n-2
Maximal conformations multiple conformations • “Free” rotation around C-C • No rotation around C=C bonds • No rotation around C=C bonds
C4H10 Projection along steric hindrance
• NOT isomers of alkanes (cyclopropane NOT an bonds, have multiple • Name ends in “-ene” • Name ends in “-yne”
the C2-C3 bond CH3 conformations
CH3 isomer of propane)
• Name ends in “-ane”

1) Identify highest priority functional

group
butane Structural formula: 2) Identify longest carbon chain
containing high priority group
Name: 3) Number the carbon chain to give
Molecular formula: lowest number to high priority
group
Minimal steric hindrance 4) Identify any substituents and their
Line structure: position on the carbon chain
or 4-Methylpent-2-yne
or 4-Methylpent-2-yne
6 7 8 11

Aromatic Hydrocarbons Naming Aromatic Hydrocarbons Alcohols and Phenols Ethers

Structural formula
representations of benzene

C6H6 = benzene if main functional group

= phenyl if substituent CH3 Br
Br Methoxymethane
(dimethyl ether)

= phenyl Cl

or 1-Butanol 2-Butanol 2-Methyl-2-propanol Methoxybenzene

1-bromo-2-methylbenzene 1-bromo-3-chlorobenzene 1,4-dibromobenzene
(methyl phenyl ether)
(o-bromomethylbenzene) (m-bromochlorobenzene) (p-dibromobenzene)
(anisole)
= benzyl
or IUPAC preferred name
2-bromotoluene
(o-bromotoluene) o = ortho = 1,2- 2-methoxypropan-1-ol
methylbenzene phenol methoxybenzene m = meta = 1,3-
(preferred IUPAC (preferred IUPAC p = para = 1,4-
name = toluene) name = anisole)
12 13 15 16

Aldehydes and Ketones R Carboxylic Acids Esters and Amides Amines and Heterocyclic Compounds
C O -oate
carboxyl group
R'
carbonyl group

Ester
replace
with –OR
-al -oic acid
IUPAC: ethanoic acid
carboxyl group
Amide -amide
replace
with –NR2
-one
pyridine

( )
17 19 20 21

R = abbreviation
Carboxylic acid -oic acid for any group Isomers continued Non-superimposable mirror images = Enantiomers
attached to the
rest of the
Ester -oate
molecule

Amide -amide Tartaric Acid- first

enantiomers to be
Increasing Priority

isolated
Aldehyde -al

Ketone -one

Alcohol -ol
Amine -amine
Alkene -ene
Dextromethorphan Levomethorphan
Alkyne -yne
Over the counter 5 times stronger than
Ether -oxy* cough suppressant morphine Limonene: D is in orange and
(Robitussin, Delsym, lemon peels. L smells like pine.
Alkyl halide none 14 DM, DexAlone, Durac) 5 6
FIGURE 26-14 Slide 2 of 75
 For organic molecules, stereoisomers can be located by looking
Enantiomers and Stereoisomers for Cs in a molecule that have four different substituents. This is Example – Chiral or achiral? Naming enantiomers Example – R or S?
called a “chiral centre.”
With few exceptions, these indicate the presence of
“stereocenters” with two distinct mirror-images. System for ranking substituents:
• Assign priority
• highest rank is highest atomic number
atom directly bonded to chiral carbon (S)-3-methylhexane
• if two directly bonded atoms are the
same, go to next atom in group
3-methylhexane
• double/triple bonds treated as multiple
Palytoxin has 64
bonds to atom type at end of multiple
stereocenters.
bond
How many can you find?
• Orient molecule with lowest-ranked group
in back
• highest-to-lowest rank goes clockwise,
named R (right)
• if it goes counterclockwise, named S
(Latin for left)
7 9 10 11

Isomers continued Stereoisomers that are NOT mirror images Diastereomers Diastereomers

13 14 15
FIGURE 26-14 Slide 12 of 75

Diastereomers Diastereomers AND Enantiomers When cis and trans fails E and Z

• What if there are more than two substituents around the double
(S,R)-2-amino-3-hydroxybutanoic acid (R,S) • Stereoisomer pairs bond in an alkene (similar case for cyclo-geometric isomers)?
that have more than • Switch from “cis” and “trans” to “Z” and “E”
one chiral carbon can • Use same priority rules as for groups for R and S
be diastereomers or - two highest priority groups on same side, called “Z”
trans-1,4-dimethylcyclohexane enantiomers - if on opposite sides, called “E”

• Depends on whether
or not the combination
of R and S centres can
be produced by mirror
(S,S) (R,R)
reflection

cis-1,4-dimethylcyclohexane
16 17 18 19

Summary Sheet - Introduction to Chemical Reactivity, Nomenclature, Boiling Points, and Water Solubility [Link]

Reactant #1 Reactant #2 Product Example Notes The Four Types of Intermolecular Bonding in Organic Chemistry •Boiling point increases with strength of the
intermolecular interactions.
H H Pd/C, H2 HH HH •Water solubility increases with polarity.
Alkene Pd/C + H2 Alkane cis addition (hydrogens go Type of
R R R R on same side of alkene) Name Interaction Found in Example Strength Notes

HCl gives rise to greatest water

Amine Acid Ammonium amines but NOT amides Ionic Attraction Salts NH4 Cl Strongest

Example Carboxylic Base

salt

Salt
R

O
NH2

EtNH2
R

O
NH3Cl
(amides are not basic on nitrogen) between
point charges δ+ O
H H
solubility (most polar)
also highest boiling points

acid (Carboxylate Ph OH Ph O EtNH3 δ−

salt) Attraction between Water, alcohols O
positively charged H carboxylic acids H H 2nd strongest 2nd greatest for effect on
Hydrogen
water solubility and boiling
1. Identify highest priority group on C1 Carboxylic Alcohol, Ester R
O

OH
MeOH
R
O

OMe Alcohols used as solvent

Bonding and negatively charged
O, N or F.
amides, amines
δ−
points
acid acid, heat H2SO4, Δ O
2. Identify highest priority group on C2 Attraction between
ketones, aldehydes,
δ+
Increases as electronegativity
O O Dipole- esters, alkyl halides, O δ− 2nd weakest
3. Determine relationship Ester Water,
acid, heat
Carboxylic
acid R OMe
H2O

H2SO4, Δ R OH
This is the reverse of the
above reaction. Dipole
dipole moments
caused by differences
in electronegativity
etc. - any molecule
with a strongly δ+
difference increases
3rd greatest for effect on water
electronegative solubilty and boiling points
a) Across = E Here we use water as solvent. element (O, N, F, Cl, Br)
Increases with surface area
(increasing length of carbon
b) Same = Z Ester Water,
base
Carboxylic
acid
O H2O O
This is called ester hydrolysis
or saponification
Van Der Waals
(London forces)
Attraction between
temporary dipoles
Hydrocarbons Name Weakest chains)
R OMe NaOH R OH worst for water solubility
(least polar)
best for solubility in non-polar
solvents (e.g. pentane)

R R OH alcohol forms on most

substituted carbon Functional Group Name Example Name
HCl # Carbons Root
Alkene Water, acid Alcohol H (Markovnikoff rule)
R CH2 R C 1 Meth- R– Alkyl Pentane
H2O H2 proceeds through carbocation
2 Eth- –OH Hydroxyl OH Pentanol or pentyl alcohol
R R Cl halide adds to most
HCl substituted carbon 3 Prop-
Alkene Strong acid Alkyl H (Markovnikoff rule) –Cl, –Br, –F, –I Halide Cl Pentyl chloride
R CH2 R C 4 But-
halide H2 proceeds through carbocation
5 Pent- –NH2 Amine NH2 Pentylamine

6 Hex- O Ether O Pentyl methyl ether

Br R R R
Br2 H Results in trans product
R H
(Z)-1,2-dichloro-3-ethyl-4-methylpent-2-ene Alkene Br2 Dibromide
R R Br
7 Hept-
–SH Thiol SH Pentane thiol
8 Oct-
R
K2CrO7 C C Alkene Pentene
Alcohol K2CrO7 Carboxylic acid OH O 9 Non-
(primary alcohol) R R
H2O O O
OR ketone OH 10- Dec-
(E)-2-chloro-3-ethyl-4-fluoromethyl-5-methylhex-3-ene (secondary alcohol)

K2CrO7
R
R C H
O
Aldehyde

O
H
Pentanal

OH O Note that secondary alcohols

R R stop at the ketone stage Ketone Butyl methyl ketone
H2O Primary carbon: attached to ONE R C R Me OR 2-pentanone
R R carbon atom
O O
R Secondary: attached to TWO Carboxylic Pentanoic acid
KMnO4 carbon atoms R C OH acid OH
Alcohol KMnO4 Carboxylic acid OH O
(primary alcohol) R R
H2O Tertiary: attached to THREE O O
OH carbon atoms
R C OR Ester OMe Methyl pentanoate
Cl2, hγ Cl Cl Free-radical reaction Quaternary: attached to FOUR
Alkyl chloride O O
Alkane Cl2, hν R Me R CCl3 (number of new C–Cl carbon atoms
Amide N-methyl pentamide
(or peroxides) bonds depends on R C NH2 NHMe
# of equivalents)
20 23 R R
Other important nomenclature terms to remember
Br2, FeBr3 Also gives 1,4 (para) product Copyright 2012
Br Br James [Link]
Br2, FeCl3 but never 1,3 (meta) product OH R R R
Benzene Aryl bromide Aug 2012, version 1.1
derivative james@masterorganicchemistry
R .com
Phenyl isopropyl
[ox] Trans Cis
R-SH RS–SR (e.g. phenyl e.g. isopropanol 1,2 1,3
Thiol "Oxidant" Disulfide 1,4
bromide) ortho meta
para
 6-1 Properties of Gases: Gas Pressure 6-1 Liquid Pressure Barometric Pressure (pressure of "outside" or atmosphere) Open-End Manometer for Pressure Difference
• Pressure is amount of force applied per unit area • Height of liquid in connected tubes indicates gas-phase pressure above liquid
- why is the liquid level in each tube the same when liquid volume in wider tube must create more downward force? • Mercury is liquid and dense – can measure large pressures with short vertical column • Open tube is at “barometric” or atmospheric pressure (can measure separately)
• With open tubes, level differences show difference in pressure above each tube • Pressure in sealed container measured as difference from barometric pressure
The Concept of Pressure F • With one closed tube (under vacuum), level difference shows absolute pressure above open
P (Pa) = gxm
= tube (against ~zero)
A A closed
(g = gravitational const.) tube
Force (if vertical from gravity) m=Vxd
open vacuum
tube
Force (N) = g (m/s2) x m (kg)
Consider:
g xVx d = g xh xAx d = gxhxd
P (Pa) =
gearth = 9.80 m/s2 A A • What is the real
Rubber base pressure in the empty
760 mm
Pressure liquid pressure is directly proportional to the liquid density (d) volume at the top of the
closed tube?
Identical mass objects: same vertical force, Force (N) and the height (h) of the liquid column, does not depend on • What height of tube of
but smaller contact area = more pressure P (Pa) = area (A) water would be needed
- greater pressure gives larger indentation Area (m2) to see a similar empty
volume?
• Width of the water column is in the V term and the A term,
so cancels out (both scale with column diameter squared)
FIGURE 6-2 Illustrating the pressure exerted by a solid • It’s the downward pressure that’s the same in each tube!
FIGURE 6-3 The concept of liquid pressure
3 4 FIGURE 6-4 Measurement of atmospheric pressure with a mercury barometer 5 FIGURE 6-5 Measurement of gas pressure with an open-end manometer 6

Units for pressure 6-2 Simple Gas Laws: Apparatus 6-2 Simple Gas Laws • 1662: Robert Boyle 6-2 Simple Gas Laws • 1662: Robert Boyle

• Liquid-tube manometers and barometers give measurements in distance units Gas-tight cylinder with weightless,
Boyle’s Law Boyle’s Law
• At fixed n and T, • At fixed n and T,
- e.g. mm Hg frictionless piston Weight changed to V is inversely related to P V is inversely related to P
• Can convert to other units vary pressure
Recall: Things to measure
• Note: Standard Pressure = 100 kPa = 750.1 mm Hg = 1.0000 bar
• Moles: relate to mass 1 1
• Volume: measure container Pa Pa
V V
• Temperature: measure in container
• Pressure: need to define and measure Height measured
for volume If P doubles, PV = a (constant) If P doubles, PV = a (constant)
• Now have pressure defined, can watch V is cut in half V is cut in half
how each variable depends on other three
P 1V 1 = P 2V 2 P1V1 = P2V2
n moles added
to cylinder

Heat to vary
temperature NASA's Glenn Research Center, Public domain, via Wikimedia Commons
7 8 FIGURE 6-6 Relationship between gas volume and pressure – Boyle’s Law 9 FIGURE 6-6 Relationship between gas volume and pressure – Boyle’s Law
[Link] 10

Animation - by NASA
6-2 Simple Gas Laws 6-2 Simple Gas Laws 6-2 Simple Gas Laws Avogadro’s Law 6-2 Simple Gas Laws Avogadro’s Law
Avogadro’s Law
• 1787: Jacques Charles Charles’ Law • 1811: Amedeo Avogadro • Avogadro’s Law demonstrated by volume change with reaction V=cn
- n changes with stoichiometry
Van • Molar volume = c
VaT
A=0.0005 mol V=cn 2H2 + O2 → 2H2O 2 moles total • At fixed T and P,
B=0.001 mol V=bT 3 moles total
C=0.002 mol note V when n = 1
• At fixed T and P,
• At fixed n and P, V is directly related to n
V is directly related to T • Unit analysis says
(measured in Kelvin) molar volume is also
1 mol gas = 22.414 L gas molar mass / density
(at 0ºC, 1 atm) (at same T and P)
Note: Gay-Lussac’s Law
- fix n and V, then • Real gases have
P is directly related to T 1 mol gas = 22.711 L gas
different molar
• Extrapolating these plots to V=0 leads to first estimates of absolute zero (at STP) volumes, “non-ideal”
11 12 FIGURE 6-8 Formation of Water – actual observation and Avogadro’s hypothesis 13 behaviour (more later)
FIGURE 6-7 Gas volume as a function of temperature 14

6-3 Combining the Gas Laws:

The Ideal Gas Equation The General Gas Equation 6-4 Applications of the Ideal Gas Equation
The Ideal Gas Equation and the General Gas Equation
• If multiple variables are changing from initial to final conditions, can use “General •Molar Mass Determination
• Boyle’s law V ∝ 1/P PV = nRT Gas Equation” to solve for some unknown variables if others are known 1. Substitute mass/molar mass for n M = molar mass
nT 2. Measure V for known mass m of a gas (e.g. at STP)
• Charles’s law V∝T V∝ • Rearrange to define R 3. Rearrange ideal gas equation to solve for molar mass (all other variables known)
P
• Avogadro’s law V∝n PV PiVi PV
R= = f f m
• Let R = proportionality constant nT niTi nfTf PV = nRT and n=
M
nT • Problem solving: if given any 3 of the 4
V=R variables, can rearrange to solve for If we hold the amount constant (ni = nf): m
P unknown variable PV = RT
• Can rearrange to familiar form
M
PiVi PV
PV = nRT = f f m RT
→ → → Ti Tf M=
PV
• Any variable that is constant from initial to final will cancel out and simplify equation
15 16 17 18
 Determine Molar Mass of an unknown gas Determine Density of a known gas 6-5 Gases in Chemical Reactions
Determine Gas Density
•A 5.000 L flask is evacuated and weighed, then filled with a gas at STP. The mass of the •What is the density at STP of propane gas? If a 5.000 L flask is filled with propane gas at • Ideal gas equation gives relationship between amount (n) and volume (V) in a
m STP, what mass of propane will be in the flask? reaction (at constant P and T)
d= KEEP IN MIND flask increases by 6.169 g. What is the molar mass of the gas?
m MP
V Molar mass = M m RT Need molar mass = M for C3H8, get 3 x 12.011 + 8 x 1.008 =d= 2 NO(g) + O2(g) 2 NO2(g)
that gas densities are M= = 36.033 + 8.064 = 44.097 g/mol V RT
typically much smaller than Use modified ideal gas equation to calculate M PV • 2 mole will be 2 molar volumes, 1 mole will be 1 molar volume.
Use modified ideal gas equation to calculate d
m those of liquids and solids. • Have constant relating stoichiometric coefficient to volume (L),
PV = RT mRT  Given m=6.169 g, V=5.000L, R = 8.3145 kPa.L/mol.K MP
M Gas densities are usually M=
PV STP gives P = 100.000 kPa, T = 273.15 K d=
RT
 R = 8.3145 kPa.L/mol.K, STP gives P = 100.000 kPa, T = 273.15 K use Law of combining volumes to rewrite reaction
expressed in grams per liter
rather than grams per 6.169 g x 8.3145
kPa∙L
x 273.15 K 44.097 g/mol x 100 kPa 2L NO(g) + 1L O2(g) 2L NO2(g)
mol∙K d= = 1.9417 g/L
milliliter. M= = 28.0209 g/mol kPa∙L Here have 5 sig figs from parameters
m MP 100 kPa x 5.000 L 8.3145 x 273.15 K
=d= mol∙K
V RT Then add
Reaction
makes
From info, we have 4 sig figs. M=28.02 g/mol - can speculate that the gas is N2 m = d x V, get 1.9417 g/L x 5.000 L = 9.708 g Start with 1L O2
2L NO2
2L NO -have 3L
From 5.000 L, we have 4 sig figs. -volume
total
back to 2L
20 2 4 3

6-6 Mixtures of Gases – partial pressures 6-6 Mixtures of Gases – partial volumes 6-6 Mixtures of Gases – mole fraction 6-6 Mixtures of Gases
• Illustrate law of partial pressures by considering mixture of H2 and He again
• Dalton’s law of partial pressures • Similar approach – can describe partial volumes • Can use partial pressure or partial volume to define mole fraction
• Each component of a gas mixture exerts a pressure that it would exert if it were in the • Each component of a gas mixture occupies a portion of the total volume • What would have been the pressure of each if it was put into the 5.0 L cylinder by itself?
container alone (same n and V).
• The total pressure of a mixture of gases is the sum of the partial pressures of the naRT nbRT Pa naRT/Vtot na Va naRT/Ptot na
components of the mixture.
Va =
Ptot
, Vb = , ….. = = = χa = = = χa
Ptot Ptot ntotRT/Vtot ntot Vtot ntotRT/Ptot ntot
Ptot = Pa + Pb +…

• Relate Ptot to total moles (ntot) by ideal gas equation and Vtot = Va + Vb +…
• Summarize mole fraction expressions: =240 kPa =610 kPa =850 kPa

ntotRT
Ptot = • Percent by volume can be expressed as: na Pa Va
Vtot = = = χa
ntot Ptot Vtot

• Of the total pressure, can think of the portion of pressure caused by each component Va Vb
(definition of partial pressure), calculated using n values for each component volume % A = ✕100% volume % B = ✕100%
Vtot Vtot • Rearrange to define partial pressure and partial volume by mole fraction
naRT nbRT FIGURE 6-12 Dalton’s law of partial pressures illustrated
Pa =
Vtot
, Pb = , ….. Pa = χaPtot Va = χaVtot
Vtot 4 6 7 9

• Example 2: A 5.0 L cylinder at 20.0 ⁰C is filled with 0.50 mol H2 and 1.25 mol He.
6-6 Capture gases over water Example 1: Determine partial pressures in a mixture Calculate the total pressure in the cylinder in kPa. Then determine the mole fraction,
6-7 Kinetic-Molecular Theory of Gases
• A 20.0 L sample of air at 98.8 kPa and 273 K contains 78.08% N2 and 20.95% O2 by vol. the partial pressure (kPa), and the partial volume (L) of each gas. ntotRT
• Traditional method of trapping gas products of reaction is over water in sealed system
Calculate the partial pressures of N2 and O2 in kPa. Ptot = • Assumptions for ideal gases
ntotRT naRT nbRT Vtot
• Gas captured is really mixture of product plus water vapour Ptot = Pa = , Pb = 1. Gas molecules (or atoms) are point-mass particles
Vtot Vtot Vtot ntot = 0.50 + 1.25 = 1.75 mol T = 273.15 + 20.0 = 293.2 K Pa = χaPtot Va = χaVtot
– introduces additional component (have mass but no volume) in constant, random,
• Partial pressure of water component estimated from the saturated vapour pressure of • Rearrange to get: n = Ptot Vtot Pa = χaPtot
tot straight line motion
water at the given temperature RT ntot = 0.8705 mol kPa∙L
Ptot = 1.75 mol x 8.3145 x 293.2 K = 853 kPa = 8.5 x 102 kPa (final 2 sig fig) 2. Molecules are separated by great distances (don’t
mol∙K
Ptot = Pbar = Pgas + PH2O Pgas = Pbar − PH2O Then get nN2 = 0.8705 x 78.08/100 = 0.6797 mol or PN2 = 98.8 kPa x 78.08/100 = 77.1kPa “see” each other except during collision)
nO2 = 0.8705 x 20.95/100 = 0.1824 mol or PO2 = 98.8 kPa x 20.95/100 = 20.7kPa 5.0 L
3. Molecules collide only fleetingly, and most of the time
shortcut
sub these into Pa equation are not colliding (only see one other molecule at a
Reaction
cH2 = 0.50 mol / 1.75 mol = 0.2857 = 0.29 cHe = 1.25 mol / 1.75 mol = 0.7143 = 0.71 time)
kPa∙L
producing gas PN2 = 0.6797 mol x 8.3145 x 273 K = 77.1 kPa (final 3 sig fig)
product mol∙K 4. Assumed to be no forces between molecules (except
PH2 = 0.2857 x 853 kPa = 2.4 x 102 kPa PHe = 0.7143 x 853 kPa = 6.1 x 102 kPa when colliding)
20.0 L
kPa∙L FIGURE 6-14 Visualizing Molecular Motion 5. Individual molecules may gain or lose energy on
PO2 = 0.1824 mol x 8.3145 x 273 K = 20.7 kPa (final 3 sig fig) collision, but total energy remains constant.
mol∙K VH2 = 0.2857 x 5.0 L = 1.4 L VHe = 0.7143 x 5.0 L = 3.6 L

FIGURE 6-13 Collecting a gas over water 10 20.0 L 2 4 2

Distribution of Molecular Speeds Measure Distribution of Molecular Speeds Maxwell-Boltzmann distribution of speeds (velocities) Maxwell-Boltzmann distribution of speeds (velocities)
• Molecules are in constant motion • Apparatus to measure distribution of molecular speeds • Maxwell and Boltzmann combine to mathematically define the speed distribution curve
• Can change T (set by oven) - see effect on O2
• Refer to speed (u), velocity independent of direction (= sum of velocity vectors) • Fraction of molecules with a particular speed = F(u) distribution at 273 K vs 1000 K
• Measure individual speeds at a point in time, determine distribution • Depends on speed (u), molar mass (M), and temperature (T, in Kelvin) • Can change M (choose different molecule) to
• Determine um=median speed, uav=average speed, urms=root-mean-square speed see effect on distribution of O2 (32 g/mol) vs H2
(2 g/mol)
FIGURE 6-15 • Follows equations relating u to M and T

Slit for entry of

particles from oven
FIGURE 6-17

What does the area under this curve mean?

3 4
u 5
FIGURE 6-16 6
 Speed and Kinetic Energy Temperature and Kinetic Energy From Kinetic Energy to Pressure From Kinetic Energy to Pressure
• Link molecular properties like speed or kinetic energy to parameters like pressure • Speed in x-direction (ux = velocity), momentum of molecule = mux , F of collision = 2mux
• Kinetic energy of any conventional particle in motion is known to be related to • Can further simplify by replacing m with M/NA (M=Molar mass):
particle mass (m) and speed (u) according to: • Ave. force of single molecule = force of collision x frequency of collisions • Travel 2L between collisions at one wall, collision frequency = ux/2L
• Speed in x-direction (ux = velocity), momentum of molecule = mux , F of collision = 2mux • Average F = 2mux ∙ ux/2L = mux2 / L note that ux2 = 1/3 u2
• Travel 2L between collisions at one wall, collision frequency = ux/2L
• Get: F = mu2 P = F = mu2 = mu2 Recall
• From earlier: 3L A 3LA 3V
• If we have many particles, each with slightly different velocities or speeds, we can ux2+uy2+uz2=u2
calculate the average kinetic energy (Ēk) of the particles Why does pressure increase when volume is
• Substitute for (urms)2 and simplify to: decreased (at const. n and T)?
• Last step: convert P from one molecule
where u2 is the mean of the velocities squared to P from N molecules (use urms)
• As volume decreases, the frequency of collisions
with all sides of a container increase
- if all particles are the same, m is constant for all, but each particle has its own u proportionately
• Expression has T and constants, can state relationship:
- can’t just replace u with uav because u2 ≠ (uav)2 L·A = V
• More collisions = more pressure
(high u squared contributes proportionately more Ek than low u squared) The Kelvin temperature (T) of a gas is directly proportional to the average
translational kinetic energy (Ēk) of its molecules: T ∝ Ēk.
- Instead, use definition of root-mean-square • If T increases, then collision force and frequency
3RT both increase = more pressure [Link]

urms = u 2 = Consider how this relates to the idea of absolute zero (0 K) Additional details – p. 224
FIGURE 6-18 A model for calculating the pressure exerted by a single molecule
M 7 8 9 10

6-8 Gas Properties Relating to the Kinetic-Molecular Theory

Ideal gas equation from kinetic energy and M-B expressions Effusion and Graham’s Law Effusion and Graham’s Law
• From Kinetic Molecular Theory: • Movement of gases: diffusion and effusion • Thomas Graham (1830) • Mixture of molecules
-note that Nm = nNAVm = nM – movement of gas from a high concentration (density) to a lower concentration - noted that small molecules move more rapidly than large molecules in diffusion and effusion
• Diffusion: lower concentration zone is filled with other gases, have mixing with collisions - tried to explain motion in general, but law applies to effusion only • From Graham’s Law:
• Effusion: lower concentration zone is empty (vacuum), gas moves without collisions • Assume no collisions during effusion: (diffusion is like mixing, has collisions)
• Since: - small orifice/pinhole (select molecules by collision frequency with wall)
- low pressure on left (not zero, but low enough so no collisions in pinhole)
- near vacuum on right (no collisions beyond pinhole to bounce back) • Generalized:
Rate of effusion
• Substituting this to the top equation: Diffusion
1 Molecular speeds
• Graham’s Law (general): Rateeffusion Ratio of Effusion times = ratio of two molar masses
MW
nRT Distances traveled by molecules
More small/fast
• Get: P= molecules effuse Amounts of gas effused. (6.25)
V
to right side
Effusion
• Rearrange it to: PV = nRT
• The ideal gas law works because at a given volume, the pressure is caused by average kinetic speed of
the gas molecules which then depends on temperature according to the Maxwell-Boltzmann function 11 2 3 4
FIGURE 6-20 Diffusion and effusion

6.9 Nonideal (Real) Gases 6.9 Nonideal (Real) Gases – van der Waals constants 6.9 Nonideal (Real) Gases – Compressibility factor
Derivation of Graham’s Law
• Non-ideal gases show deviations • van der Waals constants for real gases • Measure PV/nRT, compare with ideal value = 1 (called “compressibility”)
• From first principles, rate of effusion is proportional to average speed (uav) and density (n/V):
- consider why we use uav instead of urms here from ideal gas law. - if V decrease > expected with increased P: “more compressible”, compress. fact. < 1
• Also compressibility factors - if V decrease < expected with increased P: “less compressible”, compress. fact > 1
- measure PV/nT, compare with R
- measure molar volume at STP, • Note: done at 10 bar (1000 kPa) to • Generalize for most gases at moderate T (273 K < T < 298 K):
• From Graham’s Law: rate of effusion = constant x A x uav x n compare with ideal gas emphasize non-ideal behaviour • Low P (<100 kPa, <1 atm), close to ideal
V
• Most gases non-ideal at STP • Moderate P (1000 – 20 000 kPa, 10-200 atm),
• From Maxwell-Boltzmann (kinetic-molecular theory): - PV/nT < R • H2, He, N2, O2 compressibility still compressibility factor <1
- molar volume < ideal gas within 1% of ideal, “air” behaves • High P (>50 000 kPa, >500 atm),
n P • At lower pressure and close to ideal even at 1000 kPa compressibility factor >1
• Can rearrange ideal gas law: =
V RT higher temperature, • At T < 273 K, compress. fact. changes at lower P range
most gases close to ideal
• At T > 273 K, compress. fact. changes at higher P range
• Can substitute into overall expression for Graham’s Law:
PV/nRT Low-T
• NOTE: high-T
- N2, H2, He very close to ideal 1.00
- CO, O2 ,CH4 also ideal
• If calculating the ratio of effusion rates for two components, many terms cancel 5 to 3 sig figures 8 12 9
P

6.9 Nonideal (Real) Gases – Compressibility factor 6.9 Nonideal (Real) Gases – van der Waals equation
Example 1: Application of effusion/Graham’s Law
• Real molecules have attractive • Real molecules have non-zero molar • van der Waals equation used to better estimate behavior of gases, especially at higher P Effusion of uranium hexafluoride gas has been used to enrich the 235-isotope of uranium from a mixture of 235 and 238 isotopes.
When prepared from natural uranium, the two forms present are 235UF6 (0.700%, 349.03 g/mol) and 238UF6 (99.300%, 352.04 g/mol).
intermolecular forces, interact with each volume, repel each other when forced into
other (violates ideal assumption) n2a A 10.0 L compartment in a sealed tank was filled with 0.100 mol of standard UF6 mixture at 200.0 ⁰C. A pinhole (A=1.00x10-6 m2) was
close contact (violates ideal assumption) Pideal·Videal= nRT P+ V – nb = nRT opened into a second compartment under vacuum, and 0.0100 mol of 238UF6 effused into the second compartment in an hour.
V2
• Dominates at lower pressures • Dominates at higher pressures How many moles of 235UF6 effused into the second compartment over the same time? Determine the new composition of the two
isotopes in the second compartment.
• “Correction terms” for P and V in ideal gas equation:
• Drives compressibility factor < 1 • Drives compressibility factor > 1
n 2a
P = Pideal - n a
rearrange 2
Pideal = P + equation
V2 V2
For 235UF6, write 235U
n2/V2 is concentration squared (van der Waals predicts this dependence)
a is “attractive force” between real molecules (more later in course) Everything cancels except these…
rateeff(235U) = n(235U)/t(sec)

rearrange rateeff(238U) = n(238U)/t(sec)

Videal = V – nb equation V = Videal + nb
rateeff(235U) = n(235U)/t(sec)
Ratio:
rateeff(238U) = n(238U)/t(sec)
n is number of moles
b is “volume correction” constant, related to non-zero volume of real molecules This is a slight enrichment from
0.700%, many steps needed for Therefore:
FIGURE 6-23 Intermolecular forces of attraction FIGURE 6-22 The effect of finite molecular size -can be approximated as molar volume of the molecule in liquid form significant enrichment rateeff(235U) = n(235U)
10 11
rateeff(238U) = n(238U) 4
 What is thermochemistry? Open, Closed, and Isolated Systems Open, Closed, and Isolated Systems Open, Closed, and Isolated Systems
• Study of the heat effects that accompany chemical reac8ons.
• Concerned with the interconversion of heat, work, and
Closed systems have boundaries
energy. Isolated systems have boundaries
impermeable to the flow of ma5er,
Open systems have boundaries but energy can s;ll flow in and out, impermeable to the flow of ma5er
that permit the flow of ma5er and e.g., a covered Erlenmeyer flask and energy
• Thermochemistry is part of a broader subject known as
energy into or out of it. e.g., a thermos boOle
thermodynamics (more to learn in the winter term) that e.g., a car engine, or a beaker • mass fixed, volume can change
enables predic8ons about possible physical and chemical (such as a balloon) • mass fixed
processes and products (such as • energy can enter or leave • energy fixed–heat does not flow
• Is a given process or product possible? into or out of system (adiaba8c)

• Under what condi8ons (e.g., temperature) can a desired

process take place and a product be produced?

2 3 4 5

Different Forms of Energy Energy: SI and other units How Is Energy Exchanged? Quan8ty of Heat Energy Absorbed…Heat Capacity
• Energy is exchanged between the system and its surroundings through heat
• Energy defined as capacity to perform work (w) • From the defini8on of kine8c energy (½mv2), we get the SI units of energy: (q) and work (w): • When a system absorbs heat, its temperature usually increases
• Mechanical work results from applica8on of force over distance • The increase in temperature is directly propor8onal to the amount of heat
• Heat (q) is energy transferred by virtue of temperature gradient – associated with Joule (J) = kg m2/s2 absorbed
molecular mo8on • The propor8onality constant is called the heat capacity, Cp
• Joule demonstrated experimentally that heat (q) and work (w) are interchangeable forms • units of Cp are J/°C or J/K
of energy • (Note: units for force N = kg m/s2 , so J = Nm)
• We define the system as the part of the universe chosen for study (e.g., a reac8on flask). q = Cp × ΔT
• Kine8c energy is the energy of mo8on • We define the surroundings as that part of the universe outside of the system with which
• Poten8al energy is energy stored – by posi8on, within a spring, within a chemical bond, • Another common unit is the calorie (cal): the energy required to raise the the system interacts.
within the par8cles of a nucleus Direc8on of energy flow is important • The heat capacity of an object depends on its mass (extensive property)
1 2 temperature of 1 g of water by 1 ⁰C
EP = mgh EK = mv • Example: 200 g of water requires twice as much heat to raise its temperature by 1 °C than 100
2 1 cal = 4.184 J system gains heat system releases heat energy g of water
q (heat) + ─
• Note: the food calorie or large calorie, 1 “Cal” = 1 kcal = 1 000 cal • The heat capacity of an object depends on the type of material
system gains energy from work system releases energy by
• Example: 1000 J of heat energy will raise the temperature of 100 g of sand by 12 °C, but only
w (work) or work done on system doing work
raise the temperature of 100 g of water by 2.4 °C.
+ ─
6 7 8 9

Specific Heat Capacity Example 1 – How much heat is absorbed by a copper penny with mass 3.10 g Exothermic and Bomb Calorimeter: To measure the heat of reacNon
whose temperature rises from -8.0 °C to 37.0 °C? Endothermic ReacNons
• Measure of a substance’s intrinsic ability to absorb heat The specific heat capacity of copper is 0.385 J g-1 °C-1. The setup is called a bomb calorimeter and is usually
Step 1: Sort Information Given: Tinitial = -8.0 °C, Tfinal = 37.0 °C, m = 3.10 g
made of a sealed, insulated container filled with water.
• The specific heat capacity cp (lower case c vs. capital C for heat capacity)
is the amount of heat energy required to raise the temperature of one cp = 0.385 J/(g °C) The heat of reac8on is the heat lost or The heat of reac8on “flows” to the calorimeter (water +
gram of a substance by 1 °C (intensive property) q (in J) gained by the system aper a reac8on bomb), which causes the temperature of the calorimeter
Find:
• units are J/(g·°C) has taken place. to rise.
Step 2: Strategize Concept Plan: cp, m, ΔT q
q = mcpΔT ─ qreacNon = qcalorimeter
Relationships: q = m · cp · ΔT Reac8on system releases heat
q (exothermic)
─
• The molar heat capacity Cp,m is the amount of heat energy required to Step 3: Follow the Solution:
cP = qbomb + qwater
raise the temperature of one mole of a substance by 1 °C Concept Plan to Reac8on system gains heat
Solve the q (endothermic)
• units are J/(mol·°C)
problem
+ = (Cbomb + Cwater) ⋅ΔT

q = nCp,mΔT Step 4: Check Check: Heat capacity of the bomb

the unit and sign are correct CaO + H2O à Ca(OH)2 Heat capacity of the water Insulated
Ba(OH)2·8H2O + 2 NH4Cl
àBaCl2 + 10 H2O + 2 NH3
housing
Chapter 07, Table 7.1, Page 251 10 11 12 13

Example 2 – When 1.435 g of naphthalene, (C10H8, mol. mass = 128.17 g/mol) is burned
PracQce Example – A 74.8 g sample of copper at 143.2 °C is added to an insulated
When volume is not constant: Pressure-Volume (PV) Work Example 1. In each of the following processes, determine whether any work is done by the
in a bomb calorimeter with 2000 g of H2O, the temperature rises from 23.55 °C to system or on the system when the reaction is carried out at constant pressure in a vessel
29.22 °C. Given that Cbomb = 1.80 kJ/°C and cp = 4.184 J/(g °C) for water, what is the heat vessel containing 165 mL of glycerol (C3H8O3, density = 1.26 g/mL) at 24.8 °C. The • PV work is work that is the result of a volume change Gas formed pushes against the open to the atmosphere?
released for burning 1.00 mol of naphthalene? final temperature is 31.1 °C. The specific heat capacity of copper is 0.385 J/(g·°C). against an external pressure atmosphere.
What is the molar heat capacity of glycerol in J/(mol·°C) ? • When gases expand, DV is positive, but the system is The volume changes.
a) Decomposition of calcium carbonate to calcium oxide and carbon dioxide gas
C10H8 + 12 O2à 10 CO2 + 4H2O doing work on the surroundings, so w is negative.
CaCO3(s) à CaO(s)+ CO2(g).
q = m · cp · ΔT C3H8O3 Molar mass = 92.1 g/mol
Given: mH2O = 2000 g; cp(H2O) = 4.184 J/(g °C); Tini8al = 23.55 °C; Tfinal = 29.22 °C; • if the external pressure is kept constant Formation of a gas Dngas= +1 mol, results in an expansion, work is done on the surroundings
Pressure-volume work. b) Conversion of gaseous nitrogen dioxide to gaseous dinitrogen tetroxide
and Cbomb = 1.80 kJ/°C The heat lost by the copper = the heat gained by glycerol Work = ─ External Pressure x Change in Volume 2NO2 à N2O4 Dngas= -1 mol.
- m · cp · ΔT (copper) = m · cp · ΔT (glycerol)
Find: qreac8on per mol of C10H8 w = ─ PexDV = - Pex ´ A ´ Dh = - f ´ Dh
Work is done on the system by the surroundings
SoluNon: - qrxn = qcal = mCH2OΔT + CbombΔT -74.8 g x 0.385 J/g·°C x (31.1 °C - 143.2 °C)= (165 mL x 1.26 g/mL) x cp x (31.1 °C -24.8 °C) A piston provides c) The neutralization of a 0.100 M NaOH solution by a 0.100 M HCl solution
a closed system No pressure volume work is done (i.e. no gases are formed or consumed,
= mCH2OΔT + CbombΔT
3.23 x 103 J = 1.3 x 103 g·°C x cp cp = 2.5 J/(g·°C). that can change volume is constant to 3 sig figures or more)
= (2000 g)(4.184 J/(g °C)(29.22-23.55) °C+(1800 J/°C)(29.22-23.55) °C force its volume with
= 57653 J (keep more sig fig for intermediate step) constant P heating
So qrxn = -57653 J But this is the heat release for burning 1.435 g of C10H8, which is 1.435 g/ Now need it in units of molar heat capacity
Molar heat capacity of glycerol: Cp,m = 2.5 J/(g·°C) x 92.1g/1 mol
(128.17 g/mol) = 0.01120 mol
= 2.3 x 102 J/(mol·°C).
Heat release for burning per mol is (-57653 J)/0.01120 mol = -5.15 × 106 J/mol. 14 2 3
 Example 2: If a balloon is inflated from 0.10 L to 1.85 L against an external pressure of 101.3 kPa, how
Applying pressure with weighted pistons instead of the Example 3 (Example 7-5): Suppose a piston-closed cylinder contains 0.100 mol He at 298 K and initially has two First Law of Thermodynamics
surrounding atmosphere weights corresponding to an external pressure of 2.4 atm (see diagram left). One weight is quickly removed,
Energy is not created nor destroyed during chemical or physical processes
much volume expansion work is done (ignoring the elastic work done on the balloon rubber)? and the remaining single weight (see diagram right) corresponds to an external pressure of 1.2 atm.
The amount of heat (q) gained or lost by the system and the work (w) done on or by the
Given: Vinitial = 0.10 L, Vfinal = 1.85 L, Pex = 1.01 kPa
The force exerted by M is M x g How much work, in joules, is associated with the gas expansion at constant temperature when the weight is system are used to change the internal energy of a system (DU).
removed?
Find: w Heat gained or lost by system
Concept Plan:
Work due to gas expansion (lifting M) is
P, DV w w = - M x g x Δh
∆U = q + w Work done on the
Distance Δh = ΔV/A (A is the area of the
w = - Pex ΔV System or the surroundings
Relationships: piston)
Solution:
Internal energy change
All SI units
w = - Pex ΔV = - 101.3 kPa × 1000 Pa/kPa × (1.85-0.10) L × 1 m3/1000 L Thus, w = - M x g x ΔV/A q (heat)
system gains heat system releases heat energy
+ ─
= -177 Pa m3 = -177 J Recall: P = force/area = (M x g /A) system gains energy from work system releases energy by
w (work) or work done on system doing work
Check: + ─
P = 2.4 atm P = 1.2 atm
the unit and sign are correct Therefore: w = - PextΔV system gains energy system loses energy
(This is the usual expression for PV work!) M is suddenly removed DU + ─
4 5 6 7

• The internal energy (U) is the total amount of kinetic and potential Internal Energy (U) is a State Function But q and w are NOT state functions! Let examine this case How much work is done for the two-step process?
energy a system possesses. • The change in the internal energy (U) of a system only depends on the amount of energy In Example 3: One step isothermal expansion Now let us consider a two-step process: Initial Pext = 2.40 atm, Known:
Step 1 Step 2
in the system at the beginning and end ΔV = 1.02 L, against Pext = 1.20 atm Step 1 expands against 1.80 atm, and Step 2 against 1.20 atm. P0 = 2.40 atm, Pext1 = P1 = 1.80 atm, and Pext2 = P2 = 1.20 atm
Step 1 Step 2 V0 = 1.02 L
• A state function is a mathematical function whose result only depends on the initial
Some contributions to the internal energy of and final conditions, not on the process used Find: w1, w2, and w1 + w2
a system • Otherwise stated, the value of a state function depends on the state of the system, Solution:
and not on how the state is established Step 1: P0V0 = P1V1 to find V1
• Translational kinetic energy. V1 = 2.40 atm ´ 1.02 L / 1.80 atm = 1.36 L
• Molecular rotation. w1 = - Pext1 ´ (V1 – V0) = - 1.80 atm ´ 101.3 kPa/atm ´ 0.34 L
= - 62.0 J.
• Bond vibration. Step 2: repeat P1V1 = P2V2 to find V2
• Intermolecular attractions. V2 = 2.04 L
w2 = - Pext2 ´ (V2 – V1)
• Chemical bonds. = -1.20 atm ´ 101.3 kPa/atm ´ 0.68 L
• Electron motions. = - 82.7 J.
• Nuclear energy. P0 = 2.40 atm Pext1 = P1 = 1.80 atm Pext2 = P2 = 1.20 atm
V0 = 1.02 L Total work: w = w1 + w2 = (-62.0) + (-82.7) = - 145 J
P = 2.4 atm P = 1.8 atm P = 1.8 atm
w = −124 J from Example 3
How much work is done in this two-step expansion? The more work is done on the surroundings in the two-step
8 9 10 expansion than the one-step process (-124 J). 11

Applica3on of the First Law to Chemical and Physical Changes Applica3on of the First Law to Chemical and Physical Changes
- at constant volume - at constant pressure Enthalpy H and qP
We know that w = –Pext∆V at constant pressure:
Most reac3ons we see: At constant P: (Uf + PfVf) – (Ui + PiVi) = qP (1)
- in a beaker in a lab The state of n moles of an ideal gas is defined by P, V, and T and PV = nRT. P, V, and T
∆U = qP – Pext∆V (1)
State 1 State 2 - cooking and baking are all state variables that specify the state of an ideal gas. They are state variables for
Ui Uf
- burning wood/candles Uf – Ui = qP – (PextVf - PextVi) (2) other systems as well.
Reactants Products
- yeast making bread
∆U = Uf −Ui Since P and V are state variables and U is a state func:on, Uf + PfVf is a state func:on.
- yeast fermen3ng beer Uf – Ui = qP – PextVf + PextVi (3)
- biological processes We define a new state func:on enthalpy:
∆U = q + w - etc. (Uf + PextVf) – (Ui + PextVi)= qP (4)
H = U + PV
Reaction at constant volume in a bomb calorimeter, w = 0.
All these occur at Since Pext is constant and Pi = Pf = Pext, At constant P:
Thus, Heat transferred in a constant ambient
Three different paths leading to the same internal constant volume pressure! general form of eq. (4) can be rewriNen as ∆H = Hf – Hi = qP (2)
∆U = qrxn + 0 = qrxn = qv process appears to be a
energy change (ΔU) in a system state func:on! Therefore, ΔH can be determined by measuring the heat released or absorbed during
- values of q and w are different in all three processes Heat measured at constant volume gives (Uf + PfVf) – (Ui + PiVi) = qP (5) a constant-P process or reac3on!
12
internal energy change ∆U 2 3 4

Comparison of qv and qp 3 moles reactants 2 moles products Standard States and Standard Enthalpy of Reac3on Endothermic and Exothermic Reac3ons Example 1. The combus3on of methane, CH4, the main component of natural gas,
2 CO(g) + O2(g) 2 CO2(g) qV = ∆U = –563.5 kJ/mol has a ΔrH°= -890.3 kJ/mol. What quan3ty of heat, in kJ, is released in the complete
How does qp relate to qv? • The standard state is the state of a material at a defined set of • When ΔH is ─ve, heat is being released by the system combus3on of 1400 L methane (at 18.6°C and 102 kPa)? This is approximately the
condi:ons • Reac:ons that release heat are called exothermic reac3ons average daily household consump3on during Fall in Canada.
Remember: qv = ΔU, qp = ΔH, and ∆H = ∆U + ∆(PV)
qp = qv + ∆(PV) • pure gas at exactly 100 kPa pressure • CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l) ∆rHo = − 890 kJ mol−1 (combus:on of fuel)
Known: ΔrH°= - 890.3 kJ/mol.; so we need number of moles for CH4 in 1400 L
If the reac:on is done at constant P and T (25 oC), what is qp? • pure solid or liquid in its most stable form at exactly • C6H12O6(aq) + 6O2(g) → 6 CO2(g) + 6 H2O(l) ∆rHo = − 2801 kJ mol−1 (respira:on)
PV
qp = qv + ∆(PV) = qv + ∆(nRT) = ∆U + ∆n·RT For the above 100 kPa pressure and temperature of interest (usually 25°C) n= P = 102 kPa, V = 1400 L
RT T = 18.6 + 273.15 K = 291.8 K, R = 8.3145 kPa·L/mol·K
reac:on, ∆n = -1
• substance in a solu:on with concentra:on 1 M • When ΔH is +ve, heat is being absorbed by the system
= -563.5 kJ/mol +(-1) × 8.314 J/(mol K) × 298.15 K 102 kPa x 1400 L
• Reac:ons that absorb heat are called endothermic reac3ons n= = 58.87 mol
= –566.0 kJ/mol kPa·L
• CaCO3(s) → CaO(s) + CO2(g) ∆rHo = +178 kJ mol−1 decomposi:on 8.3145 x 291.8 K
Thus, ∆H = qp = -566 kJ/mol • The standard reac3on enthalpy, ∆rHo, is the enthalpy change of a mol·K
reac:on when all reactants and products are in their standard states • 6 CO2(g) + 6H2O(l) → C6H12O6(aq) + 6 O2(g) ∆rHo = +2801 kJ mol−1
In this example, work is done on the system by the surroundings. photosynthesis
qP = - 890.3 kJ/mol x 58.87 mol = - 5.2 x 104 kJ
∆H = ∆U + ∆ngasRT

Note: Oben, ∆(PV) is quite small compared to ∆U and ∆U ≈ ∆H

qP = qV + ∆ngasRT

From 1400 L, we assume to have 2 sig figs.

6 8
5 7
 Rela3onships Involving ΔrH and Hess’s Law Applica3on of Hess’s Law Example 2: Applica1on of Hess’s Law
Given the following informa:on: Standard Enthalpies of Forma8on
2 NO(g) + O2(g) → 2 NO2(g) ΔrH° = -173 kJ/mol (1)
• ∆rHo depends upon the way the reac:on is wriNen Hess’s Law is simply a consequence of the state func:on property of enthalpy. 2 N2(g) + 5 O2(g) + 2 H2O(l) → 4 HNO3(aq) ΔrH° = -255 kJ/mol (2)
• when reac:on is mul:plied by a factor, ∆rHo is mul:plied by that factor because ∆rHo is extensive
• The standard state is the state of a material at a defined set of condi3ons
N2(g) + O2(g) → 2 NO(g) ΔrH° = +181 kJ/mol (3)
C(s) + O2(g) → CO2(g) ∆rHo = - 393.5 KJ/mol • pure gas at exactly 100 kPa pressure
Calculate the ΔrH° for the following reac:on:
2 C(s) + 2 O2(g) → 2 CO2(g) ∆rH° = 2 × (- 393.5 kJ/mol) = - 787.0 kJ/mol
3 NO2(g) + H2O(l) → 2 HNO3(aq) + NO(g) ΔrH° = ? (4) • pure solid or liquid at exactly 100 kPa pressure and temperature of interest
½N2(g) + O2(g) → NO(g) + ½ O2 (g) ∆rHo = +90.25 kJ mol–1
N2(g) + O2(g) → 2 NO(g) ∆rHo = + 180.50 kJ mol–1
Solution: Identify in your final reaction a reactant and a product that appear only once in the provided reactions.
• usually 25°C
½N2(g) + ½O2(g) → NO(g) ∆rHo = + 90.25 kJ mol–1 NO(g) + ½O2(g) → NO2(g) ∆rHo = –57.07 kJ mol–1 They are NO2(g) and HNO3 in this case. • substance in a solu3on with a concentra3on of 1 M
This means that you must reverse (1) and then multiply it by 3/2.
• ∆rHo changes sign when the process is reversed ½N2(g) + O2(g) → NO2(g) ∆rHo = +33.18 kJ mol–1 3 NO2(g) → 3 NO(g) + (3/2)O2(g) ΔrH° =-(-173)×(3/2) = 259.5 kJ/mol (5)
Multiplying (2) by 1/2 gives:
• The standard enthalpy of forma8on, ΔfH°, is the enthalpy change for the reac3on
CO2(g) → C(s) + O2(g) ∆rHo = + 393.5 kJ/mol
N2(g) + (5/2) O2(g) + H2O(l) → 2 HNO3(aq) ΔrH° = -255/2 = -127.5 kJ/mol (6) forming 1 mole of a pure compound from its cons3tuent elements
Adding (5) and (6) results in • The elements must be in their standard states
If a process occurs in stages or steps (even hypothe:cally), the enthalpy change 3 NO2(g) + N2(g) + (5/2) O2(g) + H2O(l) → 3 NO(g) + (3/2) O2(g) + 2 HNO3(aq)
for the overall process is the sum of the enthalpy changes for the individual
• By defini3on, the ΔfH° for a pure element in its reference form and standard
• Hess’s Law: if a reac:on can be expressed as a series of steps, then the ΔrH for the 3 NO2(g) + N2(g) + O2(g) + H2O(l) → 3 NO(g) + 2 HNO3(aq) ΔrH° = 259.5 + (-127.5) = 132 kJ/mol (7)
steps state is 0 kJ/mol
overall reac:on is the sum of the ΔrH values for each step
Reverse (3): 2 NO(g) → N2(g) + O2(g) ΔrH° = - (+181 kJ/mol) = -181 kJ/mol (8)
Adding (7) and (8) gives the final targeted (4): 3 NO2(g) + H2O(l) → 2 HNO3(aq) + NO(g), 11

9 ΔrH° = 132 + (- 181) = - 49 kJ/mol 2

Slide 7 - 10

Wri8ng Forma8on Reac8ons Standard Enthalpies of Forma8on (ΔfH°) Calcula8on of Standard Enthalpies of Reac8on ΔrH° from ΔfH°
Reference Form of Pure Element
Write the forma8on reac8on for CO(g) The reac3on enthalpy for standard reactants products
• Typically, the most stable form of the element under standard condi3ons: • The forma3on reac3on is the reac3on between the forma3on reac3on is standard
Na(s), H2(g), H2O(l), Br2(l), C(graphite) elements in the compound, which are C and O: C + O → CO(g) ΔrH° = Σ ni ΔfH°(ith product) – Σ nj ΔfH°(jth reactant)
enthalpy of forma3on, ΔfH°.
• The elements must be in their standard state (298.15
C(graphite) C(diamond)
K, 100 kPa) where ni and nj are coefficients in the reac3on equa3on.
Br2(l) Br2(g) • there are several forms of solid C, but the one with
ΔfHo = 1.9 kJ/mol ΔfHº = 30.91 kJ/mol ΔfH° defined as 0 kJ/mol is graphite
C(s, graphite) + O2(g) → CO(g) Units of ΔrH° and ΔfH°: kJ/mol.
• oxygen’s standard state is the diatomic gas,
O2(gas)
• Phosphorus element is an excep3on: Red Phosphorous White Phosphorous • The equa3on must be balanced, but the coefficient of Meaning of kJ/mol for the reac3on refers to enthalpy change per
the product compound must be 1 C(s, graphite) + ½ O2(g) → CO(g) mole of reac7on (as wrieen).
P(s, white) P(s, red) ΔfHo = - 17.6 kJ/mol • use whatever coefficient in front of the reactants What are common for those
to make the atoms on both sides equal without hydrocarbons with posi7ve and nega7ve
The less stable white phosphorus is defined as the changing the product coefficient enthalpies?
reference form! ΔfHº = - 17.6 kJ/mol ΔfHº = 0 Enthalpy of forma3on is related to molecular structure
4 6
3 5

Another equivalent approach is to decompose reactant(s) into reference state, followed How to determine ΔfHo for reac9ons involving ions in solu9on?
Example 1. Determine the standard enthalpy of reac3on for the following reac3on:
by recombina3on of them into products. Then use Hess’s Law. Example 2. Calculate the enthalpy change for the following reac3on
Many chemical reac3ons in aqueous solu3on are best thought of as reac3ons between ions and best represented by
2NaHCO3(s) Na2CO3(s) + H2O(l) + CO2(g) ΔrHº = ? net ionic equa3ons. For example,
2NaHCO3(s) Na2CO3 (s) + H2O(l) + CO2(g) ΔrHº = ?
2 C2H2(g) + 5 O2(g) → 4 CO2(g) + 2 H2O(l)
Product(s) Reactant(s) Product(s)
Reactant(s)
Decomposi8on of reactant(s) Reactant(s) Enthalpies of forma3on in solu3on depend upon solute concentra3on. These data are representa3ve for aqueous
Product(s)
solu3ons at standard state (1 M). ΔfH° [1 M H+(aq)] = 0 by definition.
Solu3on: 2NaHCO3(s) 2Na(s) + H2(g) + 2C (graphite) + 3O2(g) ΔrHº = -2 x ΔfHº [NaHCO3(s)]
We can write ΔrH° in terms of ΔfH°.
ΔrH° = Σ ni Δf H°(ith product) – Σ nj Δf H°(jth reactant) Solu3on: use equa3on with ΔfH° terms
Recombina8on of products
Δ rH° = [ΔfH°Na2CO3+ ΔfH°H2O + ΔfH°CO2] – [2 ΔfH°NaHCO3]
ΔrH° = Σ ni ΔfH°(ith product) – Σ nj ΔfH°(jth reactant) Then we have

2Na(s) + C(graphite) + 3/2 O2(g) Na2CO3 (s) ΔrHº = ΔfHº [Na2CO3(s)]

Product(s) Reactant(s) ΔrHº
H2(g) + 1/2 O2(g) H2O(l) ΔrHº = ΔfHº [H2O(l)] = 4 ΔfH°(CO2) + 2 ΔfH°(H2O) – 2 ΔfH°(C2H2) – 5ΔfH°(O2)
C(graphite) + O2(g) CO2(g) ΔrHº = Δf Hº [CO2(g)]
= 4 × (-393.5) + 2 × (-285.8) – 2 × 226.7 – 5 × 0
Δ rH° = [ΔfH°Na2CO3+ ΔfH°H2O + ΔfH°CO2] – [2 ΔfH°NaHCO3]

8
= - 2599.0 kJ/mol
7 Product(s) Reactant(s) 9 10

Average Bond Enthalpies (BE) average bond enthalpies (kJ/mol)

Now we can use average bond enthalpies to es*mate enthalpy of reac8on (ΔrH°) Prac%ce problem 1: Use the Hess’s law approach to determine Prac%ce problem 2: Use average bond enthalpy data to es2mate the enthalpy change for the complete
combus2on of methane:
enthalpy change for the following reac7on:
Es3mate ΔrHo for the reac3on: average bond enthalpies (kJ/mol) CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
Average bond enthalpies are all posi8ve! 2 C2H2(g) + 5 O2(g) → 4 CO2(g) + 2 H2O(l)
Step 1: Draw the molecular (Lewis) structures for the molecules involved in the reac2on
CH4 (g) + Cl2 (g) → CH3Cl (g) + HCl (g) Use data from Table 7.2
1. Decompose each reactant into its reference state
Bond forming reac3on is exothermic
2 C2H2(g) → 4 C(s) + 2 H2(g) ΔrH° = 2(-ΔfH° for C2H2(g)) = 2×(-227.4) = -454.8 kJ/mol
2Cl(g) → Cl2(g) ΔrHo = -242 kJ/mol
Δ rH° ≈ Σ BE (broken bonds) – Σ BE (formed bonds)
5 O2(g) → 5 O2(g) ΔrH = 0 kJ/mol
Bond breaking reac3on is endothermic 2. Recombine the products from the above decomposition reactions into real products
We have to break 1 C-H bond and 1 Cl-Cl bond and reactants products
Cl2(g) → 2Cl(g) ΔrHo = +242 kJ/mol
form 1 C-Cl bond and 1 H-Cl bond 4 C(s) + 4 O2(g) → 4 CO2(g) ΔrH° = 4(ΔfH° for CO2(g)) = 4×(-393.5) = -1574.0 kJ/mol
Step 2: Determine the type and number of bonds that need to be broken for reactants
Thus, 2 H2(g) + O2(g) → 2 H2O(l) ΔrH° = 2(ΔfH° for H2O(l)) = 2×(-285.8) = -571.6 kJ/mol and the type of number of bonds that need to be formed to give products.
BE can be considered to be the
“energy” required to break one ΔrH° ≈ Σ ΒΕ (broken bonds) – Σ ΒΕ (formed bonds) 4 C-H and 2 O=O bonds need to be broken
= (413 + 242) - (328 + 431) 2 C2H2(g) + 5 O2(g) → 4 CO2(g) + 2 H2O(l) ΔrH = (-454.8) + (0) + (-1574.0) + (-571.6) = -2600.4 kJ/mol
mole of the chemical bond. NOTE: These are average bond enthalpies; the C—H bonds in 2 C=O and 4 O-H bonds will form
= -104 kJ/mol
methane, CH4, will be a bit different than the C—H bond in
chloroform, CHCl3. 11 so this will be an exothermic reac3on. 12
Step 3: Es2mate ΔH for the reac2on using the following equa2on: Enthalpies of Reac;on (ΔH) – Comparing Fuels Global and Canadian Energy Resources Petroleum and Natural Gas

Average bond enthalpies (in kJ/mol) Compare enthalpy changes of combus4on for methane and methanol: • Where did fossil fuels (coal, oil, and natural gas) come from?
Δ rH° ≈ Σ BE (broken bonds) – Σ BE (formed bonds) • ΔHcomb of methane (CH4) is -890 kJ/mol • Biomass (mainly wood) – renewable fuel, major source of • from fossilized remains of marine organisms (animals, plants, algae,
• ΔHcomb of methanol (CH3OH) is -715 kJ/mol energy in many developing countries bacteria, other microorganisms) that lived un4l approximately 500
• Coal – once a major source of energy in North America and million years ago
= 4 x (413 kJ/mol) + 2 x (495 kJ/mol) Europe, s4ll a major source in China and India • Petroleum – Composi4on varies from one loca4on to another, but mostly
4 C-H bonds 2 O=O bonds • One way to compare fuels directly is through their specific heats of combus;on
• Petroleum – replaced coal in the early 20th Century for hydrocarbon compounds containing C5 to > C25
(kJ/g)
transporta4on, linked to automobiles, later for electricity • Natural Gas – Consists mostly of methane (CH4, >90%) and some ethane
− [2 x (799 kJ/mol) + 4 x (463 kJ/mol) ] • Hydroelectric power – saturated in most developed (C2H6), propane (C3H8) and butane (C4H10)
• Though biomass (wood, alcohol, municipal waste, etc.) is a viable fuel, and has countries, expanding elsewhere
2 C=O bonds 4 O-H bonds zero net carbon emissions, fossil fuels yield more energy per unit mass, so have
• Nuclear energy – Canada and some other developed • How is petroleum refined?
been more popular (and profitable).
countries • Frac4onal dis4lla4on of crude petroleum yields the following
hXps://[Link]/energy/facts/energy-ghgs/20063 frac4ons:
= 2638 kJ/mol – 3350 kJ/mol • Geothermal – used in some loca4ons, geothermal storage
• Of fossil fuels, emphasis is on natural gas (mostly methane) over gasoline or coal becoming more important globally • Gasoline (C5 – C10);
because it is more energy dense (higher specific heat of combus4on), so lower CO2 • Kerosene & jet fuel (C10 – C18);
• Solar and wind – key renewables now cost-compe44ve,
= -712 kJ/mol emissions per unit of heat.
s4ll minor component of energy but growing faster than all • Diesel fuel, hea4ng, and lubrica4ng oil (C15 – C25),
- CO2 emissions from methane also helped by having more hydrogen
atoms in combus4on stoichiometry, so some energy is from making others • Asphalt (>C25)
Experimentally, ΔHcomb for CH4 was determined to be -890 kJ/mol. water along with CO2. • More gasoline is produced by pyroly'c (high temperature)
cracking of larger HC compounds (> C25)

Components of Gasoline Coal Hydrogen Fuel Other Alterna;ve Fuels

• Formed from fossilized plant remains (usually land-based) that have been subjected to high temperature and • Combus4on of H2 produces 2.5 4mes more energy per gram Ethanol:
pressure for many millions of years than natural gas and only produces water. • Produced by fermenta4on of sugar (from sugar cane or corn)
• Pure ethanol produces about 27 kJ/g of energy
• Coal matures through 4 stages:
• Use as fuel supplement
• Lignite, subbituminous, bituminous, and anthracite H2(g) + ½O2(g) à H2O(g); ΔH = -242 kJ • Added to gasoline (most contains ca. 10% ethanol)
• Composi4on by mass%: hXps://[Link]/watch?v=r5b6SthDbsE • Pure ethanol not suitable for motor fuel in Canada, especially in winter, because it does not
vaporize easily in cold climate.
• Lignite: 71% C, 4% H, 23% O, 1% N, and 1% S; • However, produc;on, storage and transporta;on of H2 gas pose major problems • Pure ethanol is widely used as motor fuel in Brazil where the climate is warmer and lots of
• Subbituminous: 77% C, 5% H, 16% O, 1% N, and 1% S; -may be associated with greenhouse gas emissions sugar cane is available.
• Bituminous: 80% C, 6% H, 8% O, 1% N, and 5% S;
• Anthracite: 92% C, 3% H, 3% O, 1% N, and 1% S.
• Produc;on:
Methanol:
• H2 gas is not found naturally in large amounts, must be manufactured (can be expensive) • Produced in industrial processes and fermenta4on/bioreac4on with biomass
• The rela4ve carbon content increases and those of hydrogen and oxygen decrease as coal matures.
• Exis4ng methods to produce H2 gas involve endothermic reac;ons or high temperature: • Methanol produces about 20 kJ/g of energy when completely combusted
• Bituminous is main “thermal” coal for hea4ng, anthracite more likely “metallurgical” coal for steel e.g. Steam reforma4on: CH4(g) + H2O(g) → CO(g) + 3H2(g) ΔH = +206 kJ “Blue” hydrogen • It has been used in race cars as a mixture of 85% methanol and 15% gasoline.
Electrolysis: H2O(l) → H2(g) + ½O2(g); ΔH = +286 kJ “Green” hydrogen if
• Coal contains sulfur (especially bituminous) and burning coal causes severe air pollu4on due to: electricity is renewable Biodiesel
• Storage & Transporta;on:
• Air par4culate maXer, CO and SO2 (from sulfur in coal); CO2 as greenhouse gas • a diesel fuel subs4tute used in diesel engines made from renewable materials such as:
• H2 requires a much larger container for storage and transporta4on • Plant oils: canola, camelina, soy, flax mustard, coconut, palm, hemp and sunflower;
• In atmosphere, SO2 is oxidized to SO3, which combines with water in rain and clouds • Storage or transporta4on of H2 under high pressure (say as liquefied gas) poses high explosion hazard. • Waste cooking oil: yellow or tap grease; and Other oils: fish, and algae;
(SO3 + H2O → H2SO4) to produce acid rain
Gasoline is a complex mixture of hydrocarbons (alipha4c and aroma4c), generally isomers of • Animal fats: beef or sheep tallow, pork lard, or poultry fat;
(C5 – C10). This is a gas chromatographic separa4on of gasoline, showing its many components • H2 energy per unit volume is only one-third natural gas energy under similar condi4ons • The feedstock goes through a process called transesterifica'on and consists of faXy acid
methyl esters (FAME).

Chemical Explosives Alfred Nobel’s Contribu;on Trinitrotoluene, TNT PETN (pentaerythritol tetranitrate) and RDX
• Example of Underoxidized or Fuel Rich Explosive (i.e. Not enough oxygen to form CO2)
• Swedish chemist, engineer, innovator, and armaments manufacturer with 355
• For a substance to be a chemical explosive, it must undergo a chemical reac4on that patents
2C7H5N3O6(s) → 3N2(g) + 5H2O(g) + 7CO(g) + 7C(s) ΔH = - 4184 J/g PETN • One of the most sensi4ve of the
• releases a lot of energy, making the temperature and gas pressure rise rapidly. secondary explosives and rarely used
• Most famous patent: Dynamite alone
• produces lots of gas, leading to an increase in gas pressure.
• Invented first plas4c explosive: Gelignite or ‘blas4ng gela4n’
• does this very quickly, leading to a rapid expansion of the gas. • 1.66 rela4ve effec4veness (R.E.) factor
• Became rich due to these lucra4ve patents (measurement of explosive power for
• Willed his fortunes to crea4on of the “Nobel Prizes” Alfred Nobel military purposes compared to TNT as 1) (pentaerythritol tetranitrate)
Nitroglycerine (1833-1896)
B: Protective coating • Detona4on velocity ≅ 8400 m/s
4C3H5N3O9(l) → 6N2(g) + 10H2O(g) + 12CO2(g) + O2(g) ΔH= - 9174 kJ

• Stable, insensi4ve to shock, and low toxicity RDX • Less sensi4ve than PETN
• First and most widely produced nitrate ester explosive, sensi4ve to impact
D: Electric • Osen mixed with oxygen-rich substances (e.g. ammonium nitrate) to convert the carbon • High detona4on velocity (≅ 8700 m/s)
• Produces gases with a volume 1200 4mes the original volume at room temperature and pressure. cable/fuse
A: Absorbent material (sawdust to CO or CO2, yielding more energy. • Rela4ve effec4veness factor of 1.6
• Temperature rises to about 5000 °C and produces a shock wave moving about 30 4mes speed of or diatomaceous earth) soaked in
sound – detona4on velocity ≅ 7700 m/s (Boeing X-37, 26.5 Mach. Mig-25, 2.83 Mach) nitroglycerin • Low mel4ng point (81 °C) and rela4ve safety so osen blended with other explosives.
• Detona4on velocity of ≅ 6900 m/s 2C3H6N6O6(s) → 3N2(g) + 3H2O(g) + 3CO(g) RDX (cyclotrimethylene
hXp://[Link]/watch?v=r17czTWHFmU
C: Blasting cap trinitramine)
At time of its invention (1860s), dynamite was the first safe and manageable chemical explosive.

Thermo Unit:

Formula: Variables: When to use:

Q = mc∆t Q = total heat/ enthalpy (J or kJ) If given the specific heat capacity, mass and temp. change of one
m = mass (g) substance.
Spontaneous and Non-Spontaneous Reac;ons c = specific heat capacity (J/g◦C or kJ/g◦C)
∆t = temp. change (◦C) Chemistry 105 Equation Sheet Chemistry 106 Equation Sheet
Chapter One: Gases Formula Sheet Chapter Two: Thermodynamics & Thermochemistry Formula Sheet
Work Internal Energy Heat Heat

Q = C∆t Q = total heat/ enthalpy (J or kJ) If given the heat capacity, and temp. change of one substance. ℎ °
Moles, Molar Mass, Mass Avogadros #, Moles, Molecules Density W = P ext ΔV ΔE = q + w q = C ΔT q = mcΔT
• Energy changes are important when thinking of the feasibility of a process or reac4on
Constants Constants Pressure  °1/2 # ! #
∆ ∆ ≥
C = heat capactity (J/◦C or kJ/◦C) a0 = 0.5291772059 Å Pressure  c = 2.99792458 × 108 m/s 1 atm = 760 torr *  =    ! = $
% = %&
' = ( Enthalpy Molar Enthalpy Standard Enthalpy Change

c = 2.99792458 × 108 m/s 1 atm = 760 torr *    e = 1.6021765 x 10-19 C = 101325 Pa *
∆t = temp. change (◦C)  
ΔH = ΔE + P ΔV ΔH x = ΔH ΔH°rxn = ΣH°(prod.) ΣH°(reac.)
• By knowing or being able to calculate the enthalpy change(s) involved we can determine the thermal
= RS (  −  ) F = 9.648534 × 104 C mol-1 = 406.783 in H2O =  + n
e = 1.6021765 x 10-19 C = 101325 Pa * H   [] [] Ideal Gas Law Ideal Gas Law & Molar Mass & Density
∆H = nH ∆H = total heat/ enthalpy (J or kJ) If given the molar enthalpy and the amount of one substance ɛ0 = 8.8541877 x 10-12 F/m = 406.783 in H2O _1 _2
h = 6.626 × 10-34 J·s = 14.6959 lb/in2 (psi) []
)( = !*+ $ =
'*+ Simple Calorimetry Heat Exchange Heat Exchanged By Solvent w.r.t c

energy that must be supplied or what we expect to obtain

V(r) = kB = 1.38065 × 10-23 J/K 1 torr = 1 mm Hg (at 0 °C)* t½ =
n = moles (n = cv or m/M) (mol) Note: + values mean endothermic h = 6.626 × 10-34 J·s = 14.6959 lb/in2 (psi) 4bc0 e
KB (water) = 0.51 °C/m 1 Pa = 1 kg·m-1·s-2*

.693
)
q surr = q sys q rxn = (q sol + q cal ) q sol = msol csol ΔT sol
kB = 1.38065 × 10-23 J/K 1 torr = 1 mm Hg (at 0 °C)*   t½ =
H = molar heat/ enthalpy (J/mol or kJ/mol) - values mean exothermic ,·.2 1 Pa = 1 kg·m-1·s-2*
f = 

KF (water) = 1.86 °C/m 1 bar = 100,000 Pa * ã

Boyle's Law Charles Law Combined Gas Law
Calorimeter Calibration: Option One Calorimeter Calibration: Option Two
ke = 8.987551 × 109 t½ = (1 (2 ) 1( 1 ) 2( 2
nH = mc∆t n = moles of substance reacting (n = cv or m/M) (mol) Calorimetry questions: me = 9.109383 × 10-31 kg
02
1 bar = 100,000 Pa * μ = Qr
Kw = 1.0 × 10-14 Energy ã[ç]0
7 ) 1( 1 = ) 2( 2 = = q water = q cal q cal = C cal ΔT cal = q rxn
me = 9.109383 × 10-31 kg 1 J = 1 kg·m2/s2 = 0.2390cal +1 +2 +1 +2
H = molar heat/ enthalpy of substance reacting (J/mol or kJ/mol) - if given information about a reacting substance and water mn = 1.6749273 × 10-27 kg ΔE = q + w mn = 1.6749273 × 10-27 kg 1 J = 1 V·C = 0.009869 L·atm
ln = −
Rz
+ ln 
mH2O cH2O ΔT H2O = (C cal ΔT cal )
q
C cal = ΔTrxn
• A Spontaneous process is a process that occurs in a system les to itself
Force
m = mass of water (1g = 1 mL) (remember water is present to determine the energy released or  7   cal
mp = 1.6726217 × 10-27 kg ∆Euniv = 0 mp = 1.6726217 × 10-27 kg 1 eV = 1.602 × 10-19 J Dalton’s Law of Partial Pressure Mole Fraction Partial Pressure
1 N = 1 kg·m·s-2 ln   = −  −  mH2O cH2O ΔT H2O
NA = 6.022142 × 1023 mol-1 NA = 6.022142 × 1023 mol-1 1 Watt = 1 J/s  R z z !& C cal =
c = specific heat capacity of water (J/g◦C or kJ/g◦C) absorbed by the reaction) ∆Suniv ≥  1 97 ßN9 − 97 )+ = )& + )/... 1& = )& = 1 & • )+ ΔT cal

• once started, no ac4on from outside is necessary to make the process con4nue.
1  L∙atm = . J
R = 8.31447 R = 8.31447 ln  = !+
∆t = temp. change of water (◦C) - usually asked to find the molar enthalpy (H) .23∙5
6 ∙ 7.
Power S = kB ln W .23∙5
6 ∙ 7. 1 Ampere = 1 C/s ßN9 Rz Bomb Calorimeter Heat Bomb Calorimeter Enthalpy
= 0.0820575 1 Watt = 1 J/s = 0.0820575 pX = ̶ log X q rxn = (q cal + q H2O ) = (C cal + cH2O mH2O )ΔT ΔH = ΔE + Δngases RT
m1H = m2c∆t m1 = mass of substance reacting (g) Calorimetry questions: .23∙5 q = mCΔT .23∙5
Conversions (* = exact)
Radioactivity
[é]
Average Molar Mass of Gas Mixture Avg. 34of Gas Molecule Avg. Molecule Speed

• A Nonspontaneous process will not occur unless some external ac4on is con4nuously applied
973 pH = pKa + log
= 1.987207 1 Curie (Ci) = 3.7 × 1010 1 2
H = molar heat/ enthalpy of substance reacting (J/g or kJ/g) - if given information about a reacting substance and water .23∙5 Energy w = ̶ Pext ΔV
Length disintegrations/s = 1 Bq Q = mCΔT
[ç]
$567. = 1&$& + 1/$/... Ē = 2
#ū Hess’s Law For Reaction: aA + bB →cC + dD
RH =1.0974 × 107 m-1 ΔH°rxn = [cΔH°f (C) + dΔH°f (D)] [aΔH°f (A) + bΔH°f (B)]
m2 = mass of water (1g = 1 mL) (remember water is present to determine the energy released or 1 J = 1 kg·m2/s2 = 0.2390cal ΔH = ΔE + PΔV
ey
1 in = 2.54 cm* 1 Gy = 1 J/kg ΔE = q + w 2 3*+
1 J = 1 V·C = 0.009869 L·atm 1 ft = 12 inches* Formulas ū =
c = specific heat capacity of water (J/g◦C or kJ/g◦C) absorbed by the reaction) Conversions (* = exact) 1 eV = 1.602 × 10-19 J
∆w =
z 1 yd = 3 ft* ρ = m/V
°
∆eÇN °
= ΣÑ,Üe2á $ Total Bond Enthalpy

∆t = temp. change of water (◦C) - usually asked to find the enthalpy per gram (H) Length 1 L∙atm = 101.3 J ΔG = ΔH – TΔS 1 m = 39.37 inches* 9℉
°
− ΣÑ,e79 Root Mean-Square Speed of Gas Molecule Root Mean-Square Speed of 2 Diff. Gas Molecules
T BE = ΔH°rxn = ΣH°(prod.) ΣH°(reac.)
TF = ·TC + 32 °F
1 in = 2.54 cm* 1mile = 5280feet* = 1.609km 5℃

• Is the energy change associated with the process (i.e. enthalpy) an important considera4on for establishing - usually given mass of something with an unknown molar mass ΔG = ΔG° + RT ln Q 5 °
∆eÇN ≈ Σâäe2ãN Enthalpy Change of Gas Phase Reactions
1 ft = 12 inches* ° ° ° Mass TK = ·TC + 273.15 K 3*+ ;<#=(&) $/
Formulas ∆eÇN = ΣÑ,Üe2á − ΣÑ,e79 ℃
;<#= = = ΔH°rxn = ΣT BE(reac.) ΣT BE(prod.)
∆H = sum of rxns ∆H = total heat/ enthalpy (J or kJ) Hess’s Law of Additivity: 1 yd = 3 ft* 1 lb = 453.59237 g Ptot = P1 + P2 + P3 + . . . − ΣâÑ2e.á $ ;<#=(/) $&
**heavier M in numerator**

whether the process is spontaneous or non spontaneous?

ρ = m/V °
∆eÇN ≈ Σâäe2ãN ΔH°rxn = Σenthalpies of bonds broken enthalpies of bonds f ormed
Note: different forms of H indicate the type of reaction: - if given several reactions you can manipulate them to add up 1 m = 39.37 inches*
TF =
9℉
TC + 32 °F − ΣâÑ2e.á
= 16 oz. avdp.* ú
ln   =
∆y7Ü 
 − 
 ΔG = ΔH – TΔS
Graham’s Law
1mile = 5280 feet* 1 US lb = 12 troy ounces * ú R z z ΔGrxn° = ̶ RT·ln K Boltzmann Equation (W=# of microstates) Entropy Contributions
fH = formation reaction and get the overall reaction energy 5℃
1mile = 1.609 km 1 ton = 2000 lb * PV = nRT  ΔH°  
TK =
5
TC + 273.15 K PV = nRT ln  =−  −  <@EE(&) $/ S=k ln(W ) ΔS univ = ΔS sys + ΔS surr > 0
cH = combustion reaction - remember: Mass ℃
Ptot = P1 + P2 + P3 + . . .
1 amu = 1.660538 × 10-24 g Psolv = X solv P°solv  R z z @!<ABℎ#@!D E5BDF< (E) = <@EE(/)
= $&
Volume
neutH = neutralization reaction - if you flip a reaction ∆H also flips (ie. + to -) 1 lb = 453.59237 g c = λν Cg = kHPg ΔG = ΔG° + RT·ln Q Standard Molar Entropies

4 Fe + 3 O2 → 2 Fe2O3 ∆rH° = -1648.4 kJ/mol Spontaneous - if you multiply a reaction, multiply ∆H also
= 16 oz. avdp.*
1 US lb = 12 troy ounces *
E = hν Rç zé
=
Ré zç
=√
êé
êç
1 L = 1.05669 US qt.
1 US gal = 4 US qt *
ΔTb = i·KB·m
ΔTf = i·KF·m
ΔG = ̶ nFE
w = ̶ Pext ΔV
Constants & Conversions
ΔS°rxn = ΣnS°f (prod.) ΣnS°f (reac.)
ℎ ey
∆H = ∑nfH(prod.) - ∑nfH(react.) ∆H = total heat/ enthalpy (J or kJ) Hess’s Law: 1 ton = 2000 lb * H=
 
= 128 US fl. ozs. *
Π = iMRT ∆w =
z * = 8. 314 I/4 • #FK(for Kpa) * = 0. 082507 O • 5D#/4 • #FK(for atm) * = 0. 08314 O • P5</4 • #FK(for
Entropy & Heat Flow
ΔH surr ΔH sys
Entropy & Heat Flow of System Only
ΔH sys
1 US fluid oz. = 29.5735 mL ΔS surr =
∑nfH(prod.) = sum of heats of formations of products - if only have a reaction with no other energy information 1 amu = 1.660538 × 10-24 g 7y = Rz
 1 cm3 = 0.001 L * S = kB·ln W 933 = eá  − eá  bars) T or = T ΔS sys = T >0
Ekinetic = ½ m2
Ba(OH)2Ÿ H2O(s) + NH4Cl(s) → BaCl2(s) +10 H2O(l)+ 2NH3(g) ∆rH° = + 165 kJ/mol Spontaneous As well! ∑nfH(react.) = sum of heats of formations of reactants - remember: Volume E = mc2 Rz
1 in3 = 16.4 cm3
Time
c = λν
E = hν
2
933 = 933 −
Rz
f
ln  1 bar = 100Kpa = 0.9869atm = 750torr = 750mmHg = 14.5psi Entropy of Dissolution
S solution > (S solvent + S solute )
Entropy & Gases
ΔS = S A+B mixed (S A(g) + S B(g) ) > 0
- use data booklet for heats of formations of several compounds 1 US gal = 3.7854 L = 4 US qt *
Φ = ℎL - KEelectron
e.ï =   = √
ê
1 year = 3.15569 × 107 s E = mc2 − ±   − 
=
- elements have a heat of formation of zero 1 US qt = 32 US fl. ozs. *
RS ℎ pX = ̶ log X Force A = kN 
[S  ]¨≠
Gibbs Free Energy Gibbs Equation
1 US fluid oz. = 29.5735 mL N = −P 
% efficiency = energy output x 100 % efficiency (%) If asked for %efficiency and given the energy given off and used 1 N = 1 kg·m·s-2 [A]t = -kt + [A]0 % ionization = × % ΔG = ΣG(prod.) ΣG(reac.) ΔG = ΔH T ΔS
• Clearly enthalpy change for a process is not a reliable criterion for predic4ng direc4on of spontaneous 1 cm3 = 0.001 L *  Kw = [H3O+][OH-] SçÆ
ln [A]t = – kt + ln [A]0 N±°
energy input energy output (J or kJ given off or released by a system) by a system 1 in3 = 16.4 cm3 log K =
.59

change. To beXer predict spontaneity we will need to examine another system property, Entropy! (See Ch. energy input (J or kJ used or absorbed by a system) * = exact ν = frequency  = *
© Updated 9/18/2018 BYU Department of Chemistry and Biochemistry
* = exact ν = frequency  = *
© Updated 9/18/2018 BYU Department of Chemistry and Biochemistry

13 later in course) Downloaded by Snacci (neemine329@[Link]) Downloaded by Snacci (neemine329@[Link]) Downloaded by Snacci (neemine329@[Link]) Downloaded by Snacci (neemine329@[Link])
Classical Mechanics But, why should we care? Electromagnetic Radiation Electromagnetic Spectrum
The physical theory describing the motion of macroscopic objects. Examples includes visible light, x-rays, infrared, microwaves, … Wavelength and frequency are inversely proportional

• Based on Newton’s laws of motion. Oscillation of electric (E) and magnetic (H) fields
• Interaction of forces and matter is described by through space and matter
"⃗ = $%⃗ • E & H fields are perpendicular to each other
• If we know an object’s mass ($) and the force acting • E & H fields are in phase
⃗ we can predict its acceleration (%)
on it ("), ⃗ and how We’ll focus on the electric field to analyze EM waves
it will move (determinism). characterized by:
• At the end of 19th century, there were 3 experiments ! =#$
that classical mechanics couldn’t explain which lead Speed of light (c) = 2.9979 x 108 m·s-1 (in vacuum)
to the development of quantum theory. Source: [Link] SI unit: meters/second (m/s = m·s-1)
1) Black body radiation
2) Photoelectric effect • Interactions between electrons and nuclei leads to chemical bond formation
3) Atomic spectra • Bonding dictates the structure of molecules Frequency:
Symbol: ν (nu) [NOT VEE]
All 3 experiments involved the interaction of light and • Changes in bonding drive chemical reactions Wavelength:
Source: [Link]
SI unit: Hertz or 1/seconds “CD” is a compact disk,
matter, so we first need to talk about waves. • If we want to understand chemistry, we need to understand electrons. And, for that, we Symbol: λ (lambda) (Hz = 1/s = s-1) similar to a DVD
2 need to understand quantum mechanics. 3
SI unit: meters (m) 4
-ask your parents 5

Example Interference of Electromagnetic Waves 1) Black Body Radiation 1) Black Body Radiation
Classical physics could not provide a complete explanation of light emission by heated solids. Energy is Quantized: System can only absorb or emit energy in discrete amounts called quanta.
Based on the given diagram and equation which of the following statements is true? Figure 8-5: Interference of two
overlapping light waives

! =#$
&(() ∝ +( !
Electric-stove heating element
Constructive Interference Destructive Interference
(addition of two waves) (cancellation of two waves)
Max Planck, 1900 Max Planck, 1900

Energy, like matter, Energy, like matter,

1. The frequencies of radio waves are greater than the frequencies of visible waves. is discontinuous. is discontinuous.
2. The frequencies of ultraviolet waves are greater than the frequencies of infrared waves.
3.
4.
The frequencies of gamma waves are smaller than the frequencies of X-ray waves.
None of the above statements are true. Figure 8-4: Examples of interference
E = hn E = hn
(a) Stones and ripples This Photo by Unknown Author is licensed under CC BY-SA

(b) CD/DVD reflection Molten Iron

6 7 8 9

Example 2) Photoelectric Effect 2) Photoelectric Effect 2) Photoelectric Effect

Classical wave theory could not explain the observations of the photoelectric effect. Einstein showed that the observations are expected from a particle interpretation of radiation. Einstein showed that the observations are expected from a particle interpretation of radiation.
Determine the energy, in joules, of radiation of frequency 7.39 x 1015 Hz. FIGURE 8-9
"! = Threshold Frequency Stopping voltage (Vs) is related to
What does "! depend on? the kinetic energy of photoelectrons
Physical constants:
h = 6.626 × 10-34 J s charge of electron
,#$%&%' = Φ + K. E. electron 1
Given information: ! = 7.39 × 10!" Hz $=! = ℎ : − :( = ? @*
1 2
ℎ: = ℎ:( + $) =! @* ∝ A+,-./
2
Compute energy using:

∆" = ℎ% Albert Einstein, 1905 Albert Einstein, 1905

∆" = 6.626×10!"# ,- × 7.39×10$%- !$ = 4.90×10!$&, Electromagnetic Electromagnetic

• Photoelectric Effect Phenomena: When light strikes the surface of certain metals, electrons are ejected. • When a photon of energy ℎ! strikes a bound electron in the metal’s surface: radiation has particle- • Experimental way to confirm Planck’s constant (ℎ). radiation has particle-
• No matter how intense the light, no current flows if the !#$%&' < !( . • A photoelectron is liberated if ℎ!#$%&' > Φ, where Φ (work function) like properties. • The negative potential on the grid acts to slow down the electrons. like properties.
represents the minimum energy needed to extract an electron. So, it is • Increasing the potential, a point is reached at which the photoelectrons
• For !#$%&' > !( (there is a photoelectric current no matter how weak the light):
• The # of electrons emitted (i.e., photoelectric current) depends only on the intensity of the light, but
related to threshold frequency !( through Φ = ℎ!( .
• Any energy in excess of the work function appears as the kinetic energy
Ephoton = hn are stopped. This is called stopping voltage (0!). = 1 0)
• At the stopping voltage, the kinetic energy of photoelectrons has been Ephoton = hn
10
• The kinetic energies (i.e., velocity) of the emitted electrons depend only on the frequency of light. 11 (K.E.) of emitted photoelectron. 12 converted to potential energy. 13

Example 3) Atomic Emission Spectra 3) Atomic Emission Spectra

For free proton and electron, set to E = 0, electron
bound to proton has lower energy from there 3) Atomic Emission Spectra
Radiation is emitted or absorbed by a transition of the electron from one quantum state to
Atomic spectra of Hydrogen atom is among the most extensively studied. The energy of H atom is quantized and all allowed energy values are negative.
The minimum energy required to cause the photoelectric effect in potassium metal is another.
3.69 x 10-19 J. If 420 nm radiation is shone on potassium, will electrons be ejected? If
yes, what is their velocity? Physical constants: ∆" = "' − "(
h = 6.626 × 10-34 J s ( J = kg m2 s-2) 1 1
Given information: Φ = 3.69×10-!2; me = 9.109 × 10-31 kg ∆" = −R ) * − *
8*&+'+, = 420 5= c = 2.9979 × 108 m s-1 4' 4(
and,
First, calculate the energy of a single photon: Figure 8-12: The Balmer series for hydrogen atoms – a line spectrum (only ones visible)
∆3 = ℎ! 456 7 = 8! ∆" = "+,-.-/ = ℎ 5
Niels Bohr, 1913 Niels Bohr, 1913 Niels Bohr, 1913
ℎ7 6.626×10-./ ;< × 2.9979×100 =< -!
3*&+'+, = ∆3 = ℎ! = = = 4.7×10-!2; Johan Balmer (1885) Johannes Rydberg (1888)
8 4.2×10-1 =
−R E ∆% = %L − %M −R E gives −R E
The electrons are ejected, because Ephoton > 3.69 x 10-19 J. To calculate their velocity: %D = F %D = F %D =
( ( (F
1
345 = Φ + =B3
%L − %M
2 5 = 1, 2, 3, … 5 = 1, 2, 3, … *= 5 = 1, 2, 3, …
1
4.7×10-!2; = 3.69×10-!2; + 9.109×10-.! @A B3 B = 4.8×10" =< -!
B is a constant RH = 2.179 ´ 10 −18 J RH = 2.179 ´ 10 −18 J ℎ RH = 2.179 ´ 10 −18 J
2 n and m are integers
14 18 19 20
Figure 8-13: Energy-level diagram for the hydrogen atom Figure 8-14:Emission and absorption spectroscopy
 Example Wave-Particle Duality Wave-Particle Duality Wave-Particle Duality
We looked at phenomena that can only be explained if light is quantized and has dual nature. Can matter have dual nature? In other words, does matter exhibit wave-like behaviour? Can matter have dual nature? In other words, does matter exhibit wave-like behaviour?
Determine the wavelength of light absorbed in an electron transition from n=3 to n=5
in a hydrogen atom. Atomic Emission Spectra
Physical constants: Black Body Radiation Photoelectric Effect
h = 6.626 × 10-34 J s ( J = kg m2 s-2) (Ultraviolet Catastrophe) Schematic Representation of Particle vs. Wave Diffraction
Given information: B, = 3 c = 2.9979 × 108 m s-1
B0 = 5 RH = 2.17868 × 10-18 J

First, calculate the energy absorbed:

2 2 2 2
∆, = −R 1 − = 2.17868 × 10−18 G − = 1.54928× 10−19 G Louis de Broglie, 1924 Louis de Broglie, 1924
3&' 3(' !4 5

Then, calculate the wavelength: Small particles of Small particles of

ℎK 6.626 × 10−34 GO 2.9979 × 108 $/O matter may at times Figure 8-15: Wave properties of electrons matter may at times
∆, = ℎ A = → L= = 1.282 ×10−6 $ = 1282 B$ display wavelike (a) Diffraction of X-ray by metal foil display wavelike
L 1.54928× 10−19 G What we expect for particles What we expect for waves (b) Diffraction of electrons by metal foil.
properties. Thomson & Davisson Nobel Prize (1937) properties.
21 2 3 4

Example The (Heisenberg’s) Uncertainly Principle Example Toward Quantum Mechanics

Are there any consequences to having a dual nature? How should we view electrons in an atom?
electron
a) What is the wavelength of an electron traveling one tenth the speed of light? An electron can be shown to have a speed of 2.05 × 106 m/s. Assuming that the
b) What is the wavelength of car of mass 1000 kg at 3 m/s? precision (uncertainty) of this value is 1.5%, with what maximum precision can we Bohr’s Atomic Model
Physical constants: measure the position of the electron? 1. Electrons move in circular orbits around the nucleus
ℎ ℎ h = 6.626 × 10-34 J s ( J = kg m2 s-2) Physical constants: 2. Orbitals have fixed radius and energy levels
Broglie Equation: != = me = 9.109 × 10-31 kg ℎ nucleus
$ %& ∆( ∆$ ≥
h = 6.626 × 10-34 J s ( J = kg m2 s-2)
3. An electron can move between orbits by accepting or
c = 2.9979 × 108 m s-1 me = 9.109 × 10-31 kg
4+ emitting discrete amounts of energy
6.626×10!"# + , Compute the uncertainty in momentum by first computing the uncertainty in speed: Successes: Bohr’s Hydrogen Model
1) # = = 2.426×10!$$ 0 * *
9.109×10!"$ -. × 2.9979×10& 0 , !$ /10 Werner Heisenberg • Reproduces absorption/emission spectra of hydrogen
∆" = 0.015 × 2.05 × 10! = 3.1× 10"
−$!
!=
9
+ + • Reproduces ionization potential of H atom
& )* &
∆- = * ∆" = 9.109× 10#$% /0 × 3.1× 10" = 2.8× 10#(!
h
−$!
“Wave Packet” ' '
Failures: !=
4

6.626×10!"# + , Δx Δp ≥ Maximum precision of

!) # =
1000 -.×3.0 0 , !$
= 2.21×10!"% 0 4π Then, compute the uncertainty in position: position measurement • Only works for systems with 1 electron (H, He+, Li2+, … )
−$!
= 1.9× 10#+* • Classical mechanics predicts that a circling electron will
!=
6.626×10#$" 9 +
1
Δx: uncertainty in position ℎ
Δp: uncertainty in momentum ∆2 ≥ → ∆2 ≥ → ∆2 ≥ 1.9× 10#+* continually lose energy and spiral into the nucleus.
46∆- /0 *
Try Example 8-6a from the textbook to determine Superman’s de Broglie wavelength! 4×3.14× 2.8× 10#(!
5
Figure 8-16: The uncertainty principle interpreted graphically 6 + 7 8

Wave Mechanics Wave Mechanics 1-Dimensional Particle in a Box 1-Dimensional Particle in a Box
Considering that the dual nature of electrons and the uncertainty principle, how are we to view them? Considering that the dual nature of electrons and the uncertainty principle, how are we to view them? Matter waves for a particle are all standing waves. Matter waves for a particle are all standing waves.

Schrödinger suggested that electrons (or any other particle) • Schrödinger postulated that for • The total probability of finding
a 1-dimensional box, wave a particle in a small volume of
exhibiting wavelike properties should be described by a function must correspond to a space is the product of the
mathematical function called the wave function. standing wave within the box. square of the wave function,
and the volume of interest.
Standing waves:
Nodes do not undergo displacement (#nodes = n + 1)
2- #@ ℎ@
!= . = 1, 2, 3, ⋯ Erwin Schrödinger, 1927 !? = # = 1, 2, 3, ⋯
.
8 & '@
! = %#
"# Quantum Number
:: Energy
Figure 8-18: Electron <: wave function
as a matter wave = Hamiltonian Operator
>:
Chernoff Hall
Figure 8-17: Standing waves in a string
9 Main Entrance 10 11 12

Hydrogen Atom Quantum Numbers Quantum Numbers: Notation Hydrogen Atom

Based on Schrödinger’s equation, how is the electron distributed around the nucleus? Based on Schrödinger’s equation, how is the electron distributed around the nucleus?
., ℓ, %ℓ are related to each other so you have to choose them in a specific order Notation:
• Different sub-shells are given different labels • l = 0 à label = s
'% n Principle Quantum Number Principle Shell • l = 1 à label = p '%
!!,ℓ,$ℓ ", $, % = '! " (ℓ,$ℓ $, % )! = − & + = 1, 2, 3, ⋯ • Can take on positive integer values • Labels depend on the value of l !!,ℓ,$ℓ ", $, % = '! " (ℓ,$ℓ $, % )! = − + = 1, 2, 3, ⋯
+ (n = 1, 2, 3, 4, …) • l = 2 à label = d +&
• Labels are related to the shapes of the orbitals (later slides)
• Determines the energy of the orbital • l = 3 à label = f
• R(r) describes how 3 changes as we move away from the nucleus • Determines the most probable distance of
- Called the radial function finding an electron from the nucleus

• Y(4, 5) describes how 3 changes as we move around the nucleus l Orbital Angular Momentum Quantum Number Sub Shell
• Restricted integer numbers < n Examples:
- Called the angular function • Can take on positive integer values from 0 to n-1 • To completely specify the sub-shell we also have to include • n = 3, l = 1 à 3p
• e.g. if n = 5, l = 0, 1, 2, 3, and 4 the principle quantum number, n • n = 2, l = 1 à 2p
• Determines the shape of the orbital
• 6, ℓ, 8ℓ are quantum numbers • We do this by putting n in front of the label • n = 2, l = 0 à 2s Angular
(integers with rules about relative values) ml Magnetic Quantum Number Orbital • n = 2, l = 3 à not allowed momentum
Principle
quantum number *ℓ = 0 *ℓ = -1, 0, +1 *ℓ = -2, -1, 0, +1, +2 quantum
• Determined by the value of l
Each unique set of 6, ℓ, 8ℓ will give a different wavefunction. • Can take on integer values from -l to +l Magnetic number
• e.g. if l = 3, ml = -3, -2, -1, 0, 1, 2 and 3 quantum number
13 • Determines the orientation of the orbital 14 15 16
Hydrogen Atom How do the Hydrogen orbitals look? Radial Function of Hydrogen Orbitals Angular Function of Hydrogen Orbitals
Based on Schrödinger’s equation, how is the electron distributed around the nucleus? We should look at the 3D probability density distributions of various Hydrogen orbitals.

Angular momentum & ! ., /, 0 = !!,ℓ,$ℓ ", $, % = '!,ℓ " (ℓ,$ℓ $, % # radial nodes = ! − ℓ − $ ! ., /, 0 = !!,ℓ,$ℓ ", $, % = '!,ℓ " (ℓ,$ℓ $, % # angular nodes = ℓ
quantum number (ℓ) !!,ℓ,$ℓ ", $, % = '!,ℓ " (ℓ,$ℓ $, % → !!,ℓ,$ℓ ", $, % =?
Principle s-orbitals
quantum number • have no angular dependence
(B) '% • posses 0 angular nodes
Probability densities through )! = − • %"ℓ & has its maximum at
the xz-plane for the electron +& & = 0 for s orbitals,
at different quantum whereas for other orbitals it p-orbitals
numbers for mℓ = 0. The quantum numbers are: has a zero value at & = 0. • have identical shape but
Angular Node
orient differently in space
! = 1, 2, 3, ⋯ • posses 1 angular node
See Table 8.2 for the
mathematical representation ℓ = 0, 1, ⋯ , ! − 1
of wave function and d-orbitals
probability densities. +ℓ = −ℓ, ⋯ , 0, ⋯ , +ℓ • are more complicated
• posses 2 angular nodes
Figure 8-23: Radial functions of Hydrogen Orbitals
Degenerate Orbitals
Source: [Link]
17 2 Bohr radius: a0 = 5.29177x10-11 m = 0.529177 angstrom 3 Figure 8-24: Cross-sections of the angular functions of the s, p, and d orbitals. 4

We do not expect you to know (memorize) these We do not expect you to know (memorize) these
s-orbitals of Hydrogen Atom wavefunction equations, but we show them so s-orbitals of Hydrogen Atom p-orbitals of Hydrogen Atom wavefunction equations, but we show them so
p-orbitals and d-orbitals of Hydrogen Atom
you can see where the shapes come from For s-orbitals (ℓ = 0), the $ ! only depends on &. What makes s orbitals different when n=1, 2, 3…? you can see where the shapes come from

radial function The surfaces of these 3D shapes

Simplified representation of the three 2p orbitals Simplified representation of the five 3d orbitals
represent where 95% of the
electron density is found

angular function

Size &
Maximum at nucleus # nodes
increases Wave Electron probability density of the 2px orbital. Nodal Surfaces
Figure 8-25 function
Wave function of the 1s orbital.
Figure 8-27 Zero at nucleus
Wave function of the 2px orbital. The surfaces of these 3D shapes
represents where 95% of the
Radial
electron density is found
Electron probability density of the 1s orbital. Probability

5 We expect you to know (memorize) the 3D shape of s orbitals and 6 7 8

the number of nodes in the radial distribution, but not the equations We expect you to know (memorize) the 3D shape of p orbitals and the number of nodal planes or surfaces

Electron Spin: A Fourth Quantum Number (!! ) Multielectron Atoms Penetration and Shielding Electron Configuration
The repulsion between electrons means that they stay away from one another in a multielectron atom.
Some unexplained features of the Hydrogen atom spectrum could be explained assuming that electron spins. - electrons in orbitals closer to nucleus affect energy of higher orbital electrons Electrons in orbitals closer to the nucleus screen or shield the nucleus from electrons farther away. It designates how electrons are distributed among various orbitals in principle shells and subshells.
(related to quantum entanglement – see 2022 Nobel Prize)
• Penetration: ability of electrons in s-orbitals that allows them to get close to the nucleus.
• The s-orbitals have a high probability density close to the nucleus (p- and d-orbitals have zero probability) 1. Electrons occupy orbitals in a way that minimizes the energy of the atom.
• So, electrons in s-orbitals are less screened and (on average) feel greater nuclear attraction.

%" = −
'# 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p
(! • The nuclear charge that an electron actually experiences is reduced by intervening electrons to
a value of Zeff, called the effective nuclear charge. 2. Only two electrons may occupy the same orbital, and these electrons must have
The Stern-Gerlach Experiment (1920) is an evidence that opposite spin: Pauli Exclusion Principle.
the phenomenon of electron spin exists.

In addition to the (!, ℓ, +ℓ) quantum numbers, there is a 4th quantum number:
!' Electron Spin Quantum Number Electron Spin
• Describes the orientation of the electron spin
• !! = + "⁄# or − "⁄#
3. When orbitals of identical energy (degenerate orbitals) are available, electrons
Figure 8-36) Radial
Pauli Exclusion Principle says that no 2 electrons can distribution functions: initially occupy these orbitals singly with parallel spins: Hund’s Rule.
have the same set of 4 quantum numbers in an atom. ( # ) # (()
9 10 11 12
Bohr Model (wikipedia)

The Aufbau Process Notations for Electron Configuration The Aufbau Process cont.
Example: Carbon Atom It designates how electrons are distributed among various orbitals in principle shells and subshells. Schemes for writing out electron configurations with different level of detail
Filling orbital diagrams through Row 3 and the nobel gas abbreviated electron configuration
notations

C: 6 electrons Ground State Electron Configuration of Carbon He 21 ,22-

Ground state “Electron Configuration” of
3d first 18 elements in “spdf” notation He 21 ,22.
4s Carbon: Z=6 • spdf notation (expanded): • Orbital Diagram:
He 21 ,22/
Energy (not to scale)

) )
1# 2# 2%*+ 2%,+ He 21 ,220
3p
3s • spdf notation (condensed): Core: [He] Valence
• There are only 2 p electrons
Half-filled subshells and
2p
– occupy equal-energy levels singly (Hund’s Rule) 1# ) 2# ) 2%) Core Valence filled subshells have
• spdf Nobel-gas-core abbreviated
2s • We can put them in any two 2p orbitals “special stability”.
notation (condensed): [He]: 1s2
- by convention, put them in px and py first
1s
[He] 2# ) 2%) *+ : -.- /.- /0. 1.- 10.
[Link]
13 14 15 16
 Electron Configuration & The Periodic Table Example Mendeleev’s Periodic Law (1869) Modern Periodic Table
Elements in the same group of the table have similar electron configurations. When elements are arranged in the order of increasing atomic mass, certain properties occur periodically. Similar properties recur periodically when elements are arranged according to increasing atomic number.
Write the noble-gas-core-abbreviated electron configuration of the following atoms?

• Argon (Z=18)
[Ne]3s23p6

• Calcium (Z=20)
[Ar]4s2

• Bismuth (Z=83)
[Xe]6s24f145d106p3
In Mendeleev’s table (1871), similar elements fall in vertical groups, and the properties of the
[Link]
elements (e.g., molar volume) change gradually from top to bottom in the group. He left blank
17 18 spaces for undiscovered elements. 2 4

Metals, Nonmetals, and Their Ions Size of Atoms Size of Atoms Effective Nuclear Charge
Atoms of elements in the same group have similar electron configurations. Unfortunately, atomic radius is hard to define because an atom has no precise outer boundary. Atomic radius decreases from left to right through a row and increases from top to bottom through a column. The core electrons of an atom shield or screen the valence electrons from experiencing the full nuclear charge.

Noble Gases Main-Group Metal Ions Main-Group Nonmetal Ions

• Covalent radius is one half of the distance between the nuclei
of two identical atoms joined by a single covalent bond.
Measured for an
isolated Na2 cluster
Radius Decreases
• Metallic radius is one-half the distance between the nuclei of Smallest
radii are
two atoms in contact in the crystalline solid metal.

Radius Increases
top right
as es
• van der Waals radius is similar to metallic radius except is for cre
solid samples of noble gases. s In
diu
Measured for a piece
of solid Na metal Ra Figure 9-6)
The shielding effect and effective nuclear charge, Zeff
• Ionic radius is based on the distance between the nuclei of Figure 9-4
Metallic radii for metals and covalent radii for nonmetals.
• Metals tend to lose electrons to attain • Nonmetals tend to gain electrons to ions joined by an ionic bond. Largest radii $!"" % #
noble gas electron configurations as attain noble-gas electron configurations (properly apportioned by assigning r(O22–) = 140 pm) are bottom left
Figure 9-5
Note: a : Bohr radius = 52.9 pm (text p. 337)
0 !=−
cations. Radial distribution functions for aluminum.
&#
as anions. 5 6 7 8

Effective Nuclear Charge Ionization Energy Ionization Energy

The core electrons of an atom shield or screen the valence electrons from experiencing the full nuclear charge.
Size of Ions The quantity of energy a gaseous atom must absorb to be able to expel an electron.
Ionization energies generally increase across each period (row)
Figure 9-11
- breaks in the pattern can be understood by examining electron configurations
• Cations are smaller than the A comparison of some atomic and ionic radii
Figure 9-12 Figure 9-14) First ionization energies of the 3rd-row elements. Figure 9-13) Valence electron configurations.
!!"" = ! − $ Outer electron
occupies orbitals that
atoms from which they are in picometers (pm) E = hν

extend over much formed. knocks out electron

larger distances Removing 3s
• For isoelectronic cations, the
more positive the ionic charge,
Zeff Increases

the smaller the ionic radius.

Zeff Increases
• Anions are larger than the Removing
unpaired 3p
atoms from which they are
Zeff increases, so the average distance
formed. Example: 1st and 2nd Ionization of Magnesium
decreases (same shell)
• For isoelectronic anions, the Mg(g) → Mg+(g) + e− I1 = 738 kJ Removing
more negative the charge, the With relatively few exceptions, ionization energies paired 3p
Figure 9-9 The average distance from the nucleus for the larger the ionic radius. Mg+(g) → Mg2+(g) + e− I2 = 1451 kJ increase from left to right across a period and
Figure 9-7 Effective nuclear charges. Zeff, of valence electrons. least strongly bound electron decrease from top to bottom within a group.
9 10 11 12

Electron Affinity Magnetic Properties Polarizability Atomic Properties & the Periodic Table
The energy change that occurs when an atom in the gas phase gains an electron. A key property related to electron configurations of atoms and ions is their behaviour in a magnetic field. For an atom in the vicinity of another atom, molecule, or ion, the electron cloud is distorted. (Figure 9-19) Summary

• Diamagnetic atoms or ions: • Paramagnetic atoms or ions: volume

X(g) + e– X–(g)
The First Electron Affinity of O is • All e− are paired. • Unpaired e −.
negative (more stable) due to • Weakly repelled by a magnetic field. • Attracted to an external magnetic field.
the strong electron affinity of The more unpaired electrons present, the polarizability
the neutral O atom. stronger is this attraction.
O(g) + e− → O−(g) EA = −141 kJ

The Second Electron Affinity is

Figure 9-17
positive due to the strong repulsive (a) For an isolated atom, the distribution of electronic
force between the second electron charge about the nucleus is spherical.
and the negative O ion. (b) In an electric field, the distribution of electronic
charge is non-spherical, and the centers of positive
O−(g) + e− → O2−(g) EA = +744 kJ and negative charge no longer coincide. The atom is
Figure 9-18) Polarizability of an atom is similar in
magnitude to the atomic volume calculated from
Figure 9-15) Electron affinities (kJ/mol) of main-group elements. 13 14
said to be polarized. atomic radii. 15 16
 10-1 Lewis Theory: An Overview Lewis Structures
Periodic Table of the Elements

Lewis Symbols
Ground State Electron Configurations
1A [Link] 8A

H
1

1s1 2A
©2012 Todd Helmenstine
About Chemistry

3A
6 4A 5A 6A 7A
He
1s2
2

One of the simplest methods of representing chemical bonding. A combination of Lewis symbols that represent either transfer or sharing of electrons in a chemical bond.

C 1. The chemical symbol for the element represents the nucleus and the core electrons.
3 4 5 6 7 8 9 10

Li
2
1s 2s
1
Be
2
1s 2s
2 2
B
1s 2s p
2 1
C
C
1s1s222s
2s 2pp2
2 2 2
N
1s 2s p
2 3 valence
O
2
1s 2s p
2 4 2
F
1s 2s p
2 5
Ne
2
1s 2s p
2 6

1. Valence electrons (V.E.), electrons in the outmost shell,

11 12
core 13 14 15 16 17 18
2. Dots around the symbol represent valence electrons. Place single dots on the sides
Na
[Ne]3s1

19
Mg
[Ne]3s²

20
3B
21
4B
22
5B
23
6B
24
7B
25 26 27 28
1B
29
2B
30
1s22s2p2 Al
[Ne]3s2p1

31
Si
[Ne]3s2p2

32
P
[Ne]3s2p3

33
S
[Ne]3s2p4

34
Cl
[Ne]3s2p5

35
Ar
[Ne]3s2p6

36
play a fundamental role in chemical bonding. of the symbol, up to a maximum four, then pair up dots.
For emphasis, “X” is used to show the
electron from the Na atom. Below,
K
[Ar]4s

37
1
Ca
[Ar]4s

38
2
Sc
1
[Ar]3d 4s

39
2
Ti
[Ar]3d²4s²

40
V
3
[Ar]3d 4s

41
2
Cr
5
[Ar]3d 4s

42
1
Mn
5
[Ar]3d 4s

43
2
Fe
6
[Ar]3d 4s

44
2
Co
7
[Ar]3d 4s

45
2
Ni
8
[Ar]3d 4s

46
2
Cu
10
[Ar]3d 4s

47
1
Zn
10
[Ar]3d 4s

48
2
Ga
10
[Ar]3d 4s p

49
2 1
Ge
10
[Ar]3d 4s p

50
2 2
As
10
[Ar]3d 4s p

51
2 3
Se
10
[Ar]3d 4s p

52
2 4
Br
10
[Ar]3d 4s p

53
2 5
Kr
10
[Ar]3d 4s p

54
2 6
2. Complete electron transfer from one atom to another all electrons are drawn as dots.

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
atom leads to an ionic bond. 6 •
[Kr]5s1 [Kr]5s2 [Kr]4d15s2 [Kr]4d25s2 [Kr]4d45s1 [Kr]4d55s1 [Kr]4d55s2 [Kr]4d75s1 [Kr]4d85s1 [Kr]4d10 [Kr]4d105s1 [Kr]4d105s2 [Kr]4d105s2p1 [Kr]4d105s2p2 [Kr]4d105s2p3 [Kr]4d105s2p4 [Kr]4d105s2p5 [Kr]4d105s2p6

55 56 57-71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs
[Xe]6s1
Ba
[Xe]6s2 Lanthanides
Hf
[Xe]4f 145d26s2
Ta
[Xe]4f 145d36s2
W
[Xe]4f 145d46s2
Re
[Xe]4f 145d56s2
Os
[Xe]4f 145d66s2
Ir
[Xe]4f 145d76s2
Pt
[Xe]4f 145d96s1
Au
[Xe]4f 145d106s1
Hg
[Xe]4f 145d106s2
Tl
[Xe]4f145d106s2p1
Pb
[Xe]4f145d106s2p2
Bi
[Xe]4f145d106s2p3
Po
[Xe]4f145d106s2p4
At
[Xe]4f145d106s2p5
Rn
[Xe]4f145d106s2p6 3. Sharing of electrons between two atoms leads to a C •C• For C, there are 4 valence electrons (V.E.)
87 88 89-103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
1s22s2p2 •
Fr
[Rn]7s
1
Ra
[Rn]7s
2
Actinides
Rf Db Sg Bh Hs Mt Ds Rg Cn
[Rn]5f 146d27s2* [Rn]5f 146d37s2* [Rn]5f 146d47s2* [Rn]5f 146d57s2* [Rn]5f 146d67s2* [Rn]5f 146d77s2* [Rn]5f 146d97s1* [Rn]5f 146d107s1* [Rn]5f 146d107s2*
Uut
[Rn]5f146d107s27p1*
Fl
[Rn]5f146d107s27p2*
Uup
[Rn]5f146d107s27p3*
Lv
[Rn]5f146d107s27p4*
Uus
[Rn]5f146d107s27p5*
Uuo
[Rn]5f146d107s27p6*
covalent bond.
Gilbert N. Lewis
Lanthanides
57

La Ce
58 59

Pr Nd
60

Pm
61

Sm
62

Eu
63 64

Gd
65

Tb Dy
66

Ho
67

Er
68

Tm
69

Yb
70

Lu
71
4. Electrons are transferred or shared to give each atom a (1875-1946) • Electrons involved in the bond formation are designated differently. Of course, it is
noble gas electron configuration - the octet rule (i.e.,
[Xe]5d16s2 [Xe]4f 15d16s2 [Xe]4f36s2 [Xe]4f46s2 [Xe]4f56s2 [Xe]4f66s2 [Xe]4f76s2 [Xe]4f 75d16s2 [Xe]4f96s2 [Xe]4f106s2 [Xe]4f116s2 [Xe]4f126s2 [Xe]4f136s2 [Xe]4f146s2 [Xe]4f 145d16s2

•• •• •• •• •• impossible to distinguish between electrons, so only dots are used to represent

Example 10-1
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Actinides Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr •N• • P• • As • • Sb • • Bi •
[Rn]6d17s2 [Rn]6d27s2 [Rn]5f 26d17s2 [Rn]5f 36d17s2 [Rn]5f 46d17s2 [Rn]5f67s2 [Rn]5f77s2 [Rn]5f 76d17s2 [Rn]5f97s2 [Rn]5f107s2 [Rn]5f117s2 [Rn]5f127s2 [Rn]5f137s2 [Rn]5f147s2 [Rn]5f 146d17s2

there are eight electrons in the valence shell of each • • • • • electrons:

* values are based on theory and are not verified

1s 2s 2p 3s 3p 3d atom, except hydrogen atoms that end up with two • Al •

•• •• ••
• Se I • Ar

••
••
electrons) •

••
• • •• •• • Square brackets are used to identify ions with the charge given as a superscript.
Hund’s Rule 2 3 4

Lewis Structures for Ionic Compounds 10-2 Covalent Bonding: An Introduction Coordinate Covalent Bonds Multiple Covalent Bonds
A covalent bond in which a single atom contributes both of the electrons to a shared pair. When more than one pair of electrons must be shared if an atom is to attain an octet.
• Formula unit of an ionic compound is the simplest electrically
neutral collection of cations and anions from which the Note: electrons in a bonding pair count in the
octet of both atoms sharing them (yes, they
Ammonium ion
CO2 + + (Octet not satisfied)
chemical formula of the compound can be established. get counted twice!). These Cl and O atoms all Ammonia + H+
1. The Lewis symbols of metal ions have no dots when all Na+
Cl- have satisfied octets because of the shared
valence electrons are lost bonding electrons.
2. The ionic charges of both anions and cations are shown. +

Water + H+ Hydronium ion Two double bonds

• Lewis structures of binary ionic compounds: Usually, different symbols are used for describing “bond pair” and “lone pair” electrons. (4 “bond pair” electrons between C and each O)
Example 10-2 “Lines” are used for bonds but still represent two shared electrons.
The “bond pair” electrons come from one atom, but the coordinate covalent bond is
Figure 10-1
indistinguishable from a regular covalent bond.
Portion of an ionic crystal N2 (Octet not satisfied)

No bond is 100% ionic. Note: The “full” arrow

All chemical bonds have symbol depicts movement A triple bond
some covalent character. of electron pair. (6 “bond pair” electrons between 2 N)
7 8 9
Note: The “half” arrow symbol depicts movement of individual electrons. 6

What about O2? 10-3 Polar Covalent Bonds Electrostatic Potential (ESP) Maps Electronegativity (EN)
Most chemical bonds fall between the 2 extremes of 100% ionic and 100% covalent. A way to visualize the charge distribution within a molecule. What determines the polarity of a covalent bond?
Electron density
A covalent bond in which the electrons are not shared equally between surface containing EN describes an atom’s ability to compete for electron (or electron charge density) with
95% of the charge other atoms to which it’s bonded.
< 90 K two atoms is called a polar covalent bond. density
In such a bond, electrons are displaced toward the more nonmetallic (Nearly ionic bond)
• O2 is paramagnetic (must have unpaired element resulting in partial charges on each atom.
electrons), but the Lewis structure fails to EN! ∝ $" A − $#$ A
account for it! (revisited in Chapter 11) Ei(A)
ŸŸ ŸŸ
!! A > 0 is the ionization energy of atoms A
ŸŸ ŸŸ
Electron-rich •
Non-polar Covalent Bonds: HH or H–H Cl Cl or Cl–Cl
ŸŸ

ŸŸ
ŸŸ
ŸŸ

ŸŸ

ŸŸ

regions (Polar covalent bond) A ENA

A → A+ + e-
ŸŸ ŸŸ ŸŸ ŸŸ
• Keep in mind that that merely being able to (negative ESP)
Eea(A)
write a plausible Lewis structure does not ŸŸ
Electron-poor • !"# A < 0 is the electron affinity of atoms A
prove that it is the correct electronic
Polar covalent bonds: –O
C= H–Cl regions A + e- → A-
ŸŸ
ŸŸ

ŸŸ

structure. Proof can come only through Figure 10-3 Paramagnetism of Oxygen: ŸŸ
(positive ESP)
Figure 10-5 (Non-polar covalent bond)
confirming experimental evidence. Liquid oxygen is attracted between the
poles of a magnet. 10
Figure 10-4 Determination of the ESP map for ammonia
13
11 12

Figure 10-6 Electronegativity Difference (ΔEN) 10-4 Writing Lewis Structures Skeletal Structures
Increasing effective nuclear charge Gives an insight into the amount of polar character in a covalent bond. Atoms in the structure are arranged in the order in which they are bonded to one another.
Pauling’s Electronegativities
scale based on bond energies. (Zeff)
When atoms A and B form a covalent bond, the polarity of this bond is Reviewing some of the essential features of Lewis structures: • Distinguish between central (bonded to 2 or more atoms) and terminal
In general:
determined by the absolute value of the difference between ENA and ENB, i.e., • All valence electrons of atoms must appear in the Lewis structure (bonded to just one other atom) atoms.
• Usually, all the electrons in a Lewis structure are paired o H and F are always terminal atoms
• The lower the EN, the more ΔEN = | ENA − ENB | (diamagnetic molecules) o Central atoms are usually those with the lowest electronegativity
metallic the element is, and
the higher the EN, the more • Usually, each atom acquires an outer-shell octet of electrons, especially o Carbon atoms are always central atoms
nonmetallic it is. Ionic bond for period 2 (row 2) [for Hydrogen, a full outer-shell is 2 electrons] • Molecules and polyatomic ions generally have compact and symmetrical
• Sometimes, multiple covalent bonds may be needed to complete octets structures (except for the very large number of chain-like organic molecules).
• Electronegativities decrease
from top to bottom in a group (Readily formed by C, N, O, S, and P) N O
and increase from left to right
in a period of elements Covalent bond + O O N O
ŸŸ O O
-same pattern as ionization
–O
C= H–Cl
ŸŸ

(incorrect) (correct)
ŸŸ

ŸŸ

energy and electron affinity. ŸŸ

14
ΔEN Figure 10-7 Phosphoric acid, H3PO4 Nitrate ion, NO3-
2
3
A Strategy for Writing Lewis Structures (valence)
Example 10-7 Formal Charges (FC) Example
FC arise when atoms have not contributed equal # of electrons to the covalent bonds joining them. When more than one possible Lewis structure exists, FC are used to ascertain the most satisfactory one.
Figure 10-8
Write a Lewis Structure for nitronium ion, NO2+ Calculate formal charge for the alternative Lewis structure of NO2+
Draw a Lewis structure for carbonate ion, CO32− 1
FC = #valence e− − #lone pair e− − 2
#bond pair e− +
Total # V.E.= 4+6×3+2=24 Total # of valence e– = 5 + 6 + 6 – 1 = 16 for a free atom
•• •• ••
O—N—O O N O

••
••

••
••
•• •• ••
ŸŸ ŸŸ “Do valence electrons remain?” No +
O C O + 1 Subtract # of electrons
ŸŸ

ŸŸ

O—N—O O N O FC(O) = 6 − 4 – (4) = 0

ŸŸ ŸŸ

••
••
•• •• assigned to a bonded
“Do all atoms have octets?” 2 atom in a Lewis structure
No, C doesn’t have octet + 1 1
O •• •• FC(O≡) = 6−2 – (6) = +1 FC(N) = 5−0 – (8) = +1
ŸŸ
ŸŸ

- so form a multiple bond O—N—O 1 2

FC(N) = 5 − 0 – (8) = +1 2

••
ŸŸ

••
•• ••
2
2− 1
ŸŸ + + Is there any other Lewis FC(O–) = 6−6 – (2) =−1
•• •• 2
O C O
ŸŸ

ŸŸ

O—N—O O N O formal charge of each atom

••
••

••
overall charge of the cation

••
ŸŸ ŸŸ •• •• •• •• structure possible? 0•• + •• 0 +
O=N=O•• + + -
•• ••
O O N O

••
ŸŸ
ŸŸ

••
ŸŸ ••

4 5 6 7

Which Lewis structure is plausible? Example 10-8 10-5 Resonance 10-5 Resonance
Follow general rules based on formal charges (FC) The situation in which two or more plausible Lewis structures contribute to the “correct” structure. The situation in which two or more plausible Lewis structures contribute to the “correct” structure.

Use formal charges to determine the “best” Lewis structure among Two possible Lewis structures exist for ozone, O3 :
1. Sum of FC is the overall charge of the molecule or polyatomic ion. Acceptable contributing structures to a resonance hybrid:
several possible for nitrosyl chloride (NOCl).
• Must all have the same skeletal structure (the atomic positions cannot change)
2. Where FC are required, they should be as small as possible.
0 +2 -2 -1 +2 -1 0 0 0 -1 0 1 • They can differ only in how electrons are distributed within the structure.
3. Negative FC usually appears on most electronegative elements, and
positive FC on the least electronegative atoms. Experimental evidence indicates that the two oxygen-to-oxygen bonds are the Resonance structures of carbonate ion, CO32− :
same with 127.8 pm length (intermediate between single and double bonds).
4. FC of same sign on adjacent atoms is unlikely. However, it does not mean that only the best Lewis structure can exist.
Other unlikely Lewis structures can be real as well. •• ••+ •• - - •• ••+ ••
0•• + •• 0 + O O O O O O
- +

••
••
+ + •• •• •• •• ••
O=N=O O≡N—O
••
••

•• •• •• Hydrogen cyanide Hydrogen isocyanide The true structure is a resonance hybrid of

(best) (unlikely) plausible contributing structures.
H N C

ŸŸ
Conforms to all rules Only conforms to 0 +1 -1
The three C-O bonds are equivalent.
-½ •• ••+ •• -½
the first 2 rules Best High energy molecule found O O O Electrostatic potential map of ozone
•• •• (revisit later) The ion has the same hybrid structure all the time
8
in interstellar medium 9 10 11

10-6 Exceptions to the Octet Rule 10-6 Exceptions to the Octet Rule 10-6 Exceptions to the Octet Rule 10-6 Exceptions to the Octet Rule
Case 1: Odd-Electron Species Case 2: Incomplete Octets •• •• •• Case 2: Incomplete Octets Case 3: Expanded Valence Shells
F

••
F

••
F
••
••

••

• Molecules with an odd number of electrons must have an unpaired electron

••

Boron trifluoride, BF3 Boron trifluoride, BF3 • Nonmetals of 3rd period and beyond can form stable molecules with more than 8
somewhere in the structure. Lewis theory deals with electron pairs and – +
B B B (e.g., 10 or 12) electrons around the central atom.
does not tell us where to put the unpaired electron. •• – BF3 chemical behaviour is consistent with central B atom not having a complete • Usually occurs when a nonmetal atom is bonded to highly electronegative atoms
•• F F ••
••

••
F F ••
••

••

•• F F••
••

+
••

• These molecules are known as free radicals and are highly reactive. octet, but “wanting” one.
••

••
••

••
••

••

B has incomplete octet Positive FC on the most F has a much higher PCl3 PCl5 SF6
electronegative atom electronegativity than B •• •• ••
– F
H Cl

••
•• Cl ••

••
••
BF3 has a strong tendency to ••

••
••

••
••
•• •• F F •• F ••

••
••

••

••
••
••
••
•• Cl

••
F ••

••
N=O O—H Cl •

••
(best) (unlikely) form a coordinate covalent
•

H—C—H •• •• •• – •• •• P P • S

••
bond with species capable of F B F B F

••

••
••
••
•• ••
•

••
Usually, we complete octets and then minimize formal charges, however, in this case that gives a •• •• F F•

••
•

••
••Cl Cl •

••
••
••Cl Cl •

••
Nitrogen monoxide donating electron pair to B. •• F F•• F •

••

••
••
Methyl radical Hydroxyl radical •

••
•

••
••
+ve charge on F and a –ve charge on a neighbouring B, which is extremely against electronegativities

••
••

••
••
(Unpaired electron is F ••

••

••
••
••
placed on N to get a • In this extreme case, EN wins over completing octets and structure with 0 formal charges is best ••
structure free of FC) • Note the electrostatic potential map agrees with the left-most structure and not with the other two octet expanded valence shell expanded valence shell
12 13 13 14

Example Shapes of Molecules Shapes of Molecules Valence-Shell Electron Pair Repulsion (VSEPR) Theory
The geometric figure obtained when joining the nuclei of bonded atoms by straight lines. The geometric figure obtained when joining the nuclei of bonded atoms by straight lines.

Draw Lewis structure of sulfate ion, SO42− Water, H2O Bond angle
Hydrogen peroxide, H2O2 Bond length Electron pairs repel each other, whether they are in chemical bonds
angle between adjacent bonds distance between directly (bond pairs) or unshared (lone pairs). Electron pairs assume orientations
bonded nuclei about an atom to minimize repulsions.
: :

H:O:H
: :
: :

H:O:O:H or

Repulsion Trend:
lone pair – lone pair > lone pair – bond pair > bond pair – bond pair
Bond length Torsional angle (dihedral angle)
Better structure because it distance between directly angle between two bond vectors Ronald Gillespie
1. reduces formal charges. bonded nuclei There are two ways to describe the geometry of a molecule:
2. agrees with experimental evidence. • Electron-Group Geometry – distribution of electron groups (predicted by VSEPR)
! = 104.45°
Figure 10-10) Geometrical shape of a molecules • Molecular Geometry – distribution of atomic nuclei (the actual molecular shape)
Draw resonance structures and calculate formal charges. d1 = d2 = 95.8 pm Bond angle
15
2 angle between adjacent bonds 3 4
Representations See Petrucci text Fig 10-12
Applying VSEPR Theory Example Note: another example of incomplete octet. Possibilities for Electron-Group Geometry
Focus on pairs of electrons in the valence electron shell of a central atom in a structure. If we made double bonds to fill octet then
Name/Molecular Formula: ammonia/NH3 Water/H2O we would have a Be2- next to two Cl+, so

1. Draw a plausible Lewis structure. What is the molecular structure of BeCl2? formal charge wins over octet (like BF3) 2 electron groups AX2 linear
octahedral trigonal bipyramidal
Lewis Structure: 3 electron groups AX3 trigonal planar
2. Determine the number of electron groups around the central atom
ŸŸ ŸŸ
AX2E
Cl Be Cl

ŸŸ

ŸŸ
ŸŸ
1. Draw a plausible Lewis structure.

ŸŸ
3D Structure: and identify them as bond pairs (X) or lone pairs (E). ŸŸ ŸŸ
4 electron groups AX4 tetrahedral
3. Establish the electron group geometry (both X and E). 2. Determine the number of electron groups around the central atom AX3E
Dashed-wedged line and identify them as bond pairs (X) or lone pairs (E). AX2 AX2E2
structure: 4. Determine the molecular geometry (only consider X).
5 electron groups AX5 trigonal
3. Establish the electron group geometry (both X and E). linear
AX4E bipyramidal
4. Determine the molecular geometry (only consider X). linear AX3E2
Molecular Geometry: trigonal pyramidal bent or V-shaped AX2E3
6 electron groups AX6 octahedral Figure 10-13
Electron Group Geometry: tetrahedral tetrahedral Cl Cl
AX5E
Be trigonal planar tetrahedral
A=central atom AX4E2
VSEPR Notation: AX3E X=bond to atom AX2E2
E=electron lone pair 5 6 7 8

Electron-Group Geometry & Molecular Geometry Electron-Group Geometry & Molecular Geometry Electron-Group Geometry & Molecular Geometry

Are the bond equatorial

position
angles the same?

Which lone pair

No other potential molecular geometries position is correct?

In VSEPR Notation: The molecular geometry is the same

• A=central atom as the electron-group geometry only axial
position
• X=bond and when all electron groups are bond
terminal atom pairs.
• E=electron lone pair 9 10 11 12

How do we deal with multiple covalent bonds? Molecules with More Than One Central Atom Example
Each multiple covalent bond constitute one group of electrons as all bond pairs are confined to the same region. Determine the electron-group geometry and molecular geometry of chlorate ion, ClO3−.
(1) Total number of valence electrons = 7 + 3x6 + 1 = 26
Looking at CO2: What about ozone, O3? The geometric distribution of terminal atoms around each central atom
One electron group (2) Skeletal structure
must be determined and the results then combined into a single O O O
: :
O
:
O O
:

:
:
:
: :
description of the molecular shape around that central atom.

:
or

:
•• ••+ ••- - •• ••+ •• Cl Cl Cl
O O O O O O
••
••

(3) add electrons to (4) 3 bond pairs + 9 lone pairs = 24 electrons

•• •• •• ••
VSEPR notation: AX2 (linear) O terminal atoms :O: Remaining V.E.=26 – 24 = 2 on central atom :O:
Example 10-12

:
180°
Electron-group geometry: linear AX2E O
(5) At first glance, it appears to satisfy the octet rule. Now need to check formal charges.
Molecular geometry: linear (molecule is bent) C Cl atom valence shell can be expanded to remove some unfavorable formal charges.
Methyl isocyanate N
Looking at SO2: CH3NCO 120°
(trigonal planar) -1 -1
•• + 0 0 Electron group: AX3E
•• : : :
•• + O O O O

:
VSEPR notation: AX2E Electron group geometry is tetrahedral, but the

:
S
: :
S S

:
H H
– molecular geometry is trigonal pyramidal.

:
Example 10-10 Electron-group geometry: – Cl (6) add multiple Cl
••

O H
••

••

O O O•• O +2 0
••
••

O
••

Polyatomic anion 109° bonds to reduce

••

trigonal planar
••
••

••

Note: get AX3E for both of these, so don’t need to

••

••
••

ICl4- (tetrahedral) -1 :O: formal charges -1:O: correct formal charges to get correct geometry
Molecular geometry: bent

:
13 14 16
Expanded valence shell on Cl

Example 10-11 Molecular Shape and Dipole Moments Molecular Dipole Moment Depends on Shape Example
Treat individual bond dipole moments as vectors.
Determine the molecular shape of formamide, HC(O)NH2.
Draw structures for both cis and trans-dichloroethane and determine the
In the HCl molecule, Cl is
(1) Recall the functional group in Orgo. Draw the Lewis structure more electronegative, so δ+ δ− δ+ and δ− are the partial position of the molecular dipole.
charges on the atoms across
O H pulls more electron
:

H Cl a polar covalent bond

:

density toward it causing (not to be confused with

:

C N a polar covalent bond. “formal charges”)

Total dipole moment
CO2 is non-polar. μ=0D H2O is polar. μ = 1.85 D Cl Cl Cl H
H H
(2) So, on the C, it is AX3 (so trigonal planar). On the N, it is AX3E (so trigonal pyramidal). We use the cross-base arrow to C C C C
This is the correct answer for Lewis structure-based geometry. indicate a polar covalent bond. μ = 1.08 D
H H H Cl
In reality, the molecule is more planar than expected. Can you explain?
cis-dichloroethylene trans-dichloroethylene
Dipole moment, μ, describes the extent of charge displacement in a polar covalent bond:
- μ = 1.89 D μ=0D
O O H One resonance structure has
: :

H
:

+ ! = #×% Unit = Coulomb Ÿ meter

:

both C and N with AX3 (planar)

C
:

N C N Overall molecule is closer to 3.34×10-30 C Ÿ m = 1 D (Debye)

CCl4 is non-polar. CHCl3 is polar.
H H H H planar! 2 3 4
 Detect and Measure Molecular Dipole 10-8 Bond Order 10-8 Bond Length Average Bond Energies
The average of bond-dissociation energies for a number of different species containing the particular bond.

• Bond Order describes whether a covalent bond is single, double, or triple. • Bond length is the distance between
This is denoted by the # of shared electron pairs in a chemical bond. the centres of two atoms joined by a
covalent bond.
oSingle bond, bond order = 1
oDouble bond, bond order = 2
oTriple bond, bond order = 3 • The length of covalent bond between
two atoms can be approximated as the
Figure 10-15) Polar molecules in • In some unusual molecules, it is also possible to have bond order greater sum of their covalent radii.
an electric field than 3 (e.g., transition metals.)
• In general, for bond length:
•• •• ••
H Cl O O N N

•••

••

••

••

••
•
a. When the field is off, the molecules orient randomly single bond > double bond > triple bond
b. When the field is on, the molecules orient so that the negative Typical units: • Values are approximate measures of the strength of a particular type of chemical bond.
Bond Order = 1 2 3
ends of the molecules are toward the positive plate and vice versa. • pm, picometer (10-12 m) • In general, for bond energy : single bond < double bond < triple bond
5 8 • Å, Angstrom (10-10 m) 9 12

Bond Order/Length and Resonance 10-9 Bond Energies (BE) Calculating Enthalpy of Reaction from Bond Energies Example
Example of using bond energies in thermochemistry.

• When molecules display resonance, fractional bond orders are possible. • Bond dissociation energy, D, is the quantity of energy required to Use bond energies to estimate the enthalpy change for the reaction
break one mole of covalent bonds in a gaseous species. D can be ΔHrxn = S ΔH(bond breakage) + SΔH(bond formation)
• The bond order becomes the average of the bonds between the atoms 2H2 (g) + O2 (g) à 2H2O (g) H-H 436 kJ/mol
experimentally determined. ≈ S BE(reactants) − S BE(products)
from each resonance structure. O=O 498 kJ/mol
H H HŸ + HŸ D = 435.93 kJ/mol H-O 464 kJ/mol

ŸŸ
Normal CO Bond lengths:
C-O 143 pm • For H-O-H, breaking the two O-H bonds sequentially requires
C=O 120 pm slightly different energies. Break 1 O=O + 2 H-H => 498 kJ/mol + (2 x 436 kJ/mol) = 1370 kJ/mol absorbed
Example 10-15 Form 4H-O => (4 x 464 kJ/mol) = 1856 kJ/mol released
Carbonate CO bond length: H-O-H H + O-H D = +498.7 kJ/mol
129 pm ΔHrxn ≈ (414 + 243) − (339 + 431) = −113 kJ/mol < 0
O-H O+H D = +428.0 kJ/mol ΔHrxn ≈ S BE(reactants) − S BE(products)
So, this is an exothermic reaction.
(1 + 1 + 2) bonds
=
4 • The O-H bond energy in H2O is defined as the average of these When ΔHrxn > 0, the reaction is called endothermic.
ΔH = 1370 kJ/mol – 1856 kJ/mol = -486 kJ/mol
average bond order = = 1⅓
(3) structures 3 two D values (463.4 kJ/mol).
10 11 13 14
(We’ll learn more later in the unit on Thermochemistry)

Chemical Bond Theories Chemical Bond Theories Bond Formation between two hydrogen atoms Bond Formation between two hydrogen atoms
What interactions occur as two hydrogen atoms approach from an infinite distance? What interactions occur as two hydrogen atoms approach from an infinite distance?

Lewis theory is useful for many • Valence Bond (VB) Theory • Molecular Orbital (MO) Theory
purposes, including using (this lecture) (next lecture) • When two H atoms are
electronic configuration of far apart, the potential
atoms and valence electrons to HŸ HŸ energy (P.E.) is zero.
explain chemical bonding. Lewis symbol
D
• As atoms approach each
It is not easy to combine Lewis other, each electron is
theory with Atomic Orbital
attracted to the nucleus
theory to explain simple
molecular properties such as of the other atom, while
molecular geometry. Lewis structure
repulsions also occur
H H

ŸŸ
P. E. minimum
between electrons and
between nuclei.
109.5°
We need a better model!
internuclear separation
Figure 11-2 Energy of interaction of two hydrogen atoms plotted for internuclear separations from zero to infinity
2 3 Figure 11-1 Type of interactions between two hydrogen atoms 4 5

11-2 Valence-Bond (VB) Theory Using the VB method to describe a molecular structure How can VB explain tetrahedral molecules? 11-3 Hybridization of Atomic Orbitals
VB method is a description of covalent bond formation in terms of atomic orbital overlap. Our description of geometry based on overlap of unmodified AO do not conform to observed measurements.

• A covalent bond is normally created by the overlap of half-filled orbitals on 1. Identify the valence orbitals of the central atom
two atoms (or sometimes overlap of a filled orbital on one atom and an • Example 1: CH4 transformation
109.5°

2. Sketch the valence orbitals

empty orbital on another if coordinate covalent bonding). o C forms 4 bonds with H atoms.
• This is a localized electron model of bonding: Core electrons and lone-pair 3. Bring in atoms to be bonded to the central atom & sketch orbital overlap o VSEPR gives tetrahedral geometry.
valence electrons stay in the same orbital locations as in the separated 4. Describe the resulting structure o p-orbitals don’t give tetrahedral
atoms, but the bonding electrons do not. bond angles. Modified Atomic Orbitals

3pz z
3px
• Hybridization is the (mathematical) process of transforming pure atomic orbitals into
H H H2 reformulated atomic orbitals for bonded atoms. The new orbitals are called hybrid
Example: For each H atom, there is one Lewis structure
electron in the 1s AO (half-filled).
3py orbitals, which are still atomic orbitals. The number of hybrid orbitals equals the
ŸŸ y number of pure atomic orbitals reformulated.
Covalent bond between two H atoms is
H–S–H
ŸŸ
px is filled • Example 2: O2
formed by overlap (interpenetration) of x • Hybrid orbitals are an after-the-fact rationalization of the experimentally observed
Electron density is greatest px py pz o How O2 can have unpaired Ground state O molecular shape (can we force the orbitals to match the known geometry).
two 1s orbitals. between atoms
Figure 11-4) Bonding H2S represented Observed H-S-H bond angle electrons (be paramagnetic)?
(red color in ESP) by atomic orbital overlap is close to 90° 2s 2p • Extended VB theory: covalent bonds are formed by overlap of pure or hybrid atomic
6 7 8 orbitals, which ever gives the correct shape. 9
 sp3 hybridization sp3 hybridization sp2 hybridization sp hybridization
Example: Carbon atom in CH4 Example: Nitrogen in NH3 and Oxygen in H2O Hund’s rule also applies for hybrid orbitals Example: Boron atom in BF3 Example: Beryllium atom in BeCl2

• 1 s + 3 p orbitals give 4 sp3 hybrid orbitals. sp3 Hybridization in nitrogen Tetrahedral

• 1 s + 2 p gives 3 sp2 orbitals. • 1 s + 1 p gives 2 sp orbitals.
(5 valence electrons): electron-group geometry Trigonal planar
• Each sp3 hybrid orbital has 25% s character Figure 11-7 electron-group geometry Linear
• Each sp2 orbital has 33% s • Each sp orbital has 50% s electron-group geometry
and 75% p character, so its energy is character and 66% p character. character and 50% p character.
intermediate between those.

Ψ(sp3) = Ψ(s) + aΨ(px) + bΨ(py) + cΨ(pz)

sp3 Hybridization in oxygen Lone pairs are in The 2pz remains unhybridized
(6 valence electrons): sp3 hybrid orbitals
109.5° of oxygen

O-H bond is formed between an oxygen

Pure AO 10 sp3 hybrid orbital and an H 1s orbital 11 Pure AO Hybrid AO 13 The 2pz and 2py remain unhybridized 14
Hybrid AO

11-4 Multiple Covalent Bonds 11-4 Multiple Covalent Bonds What about trigonal bipyramidal and octahedral structures? Hybrid Orbitals and Valence-Shell Electron-Pair Repulsion (VSEPR) Theory
Two different types of orbital overlap occur when multiple bonds are described by the VB method. Two different types of orbital overlap occur when multiple bonds are described by the VB method. We need to go beyond s and p subshells of the valence shell to include d-orbital contributions.
• For 3rd and 4th period elements, atomic d orbitals can be involved in hybridization. Steps in the determination of hybrid orbitals from a molecular formula.
• Example: C2H4 • Example: C2H2
H H H C C H • This is related to molecules with expanded valence shells. (1) Write a plausible Lewis structure.
o Lewis theory tells us it has a double bond o Lewis theory tells us it has a triple bond
C C Example: PCl5 Example: SF6
o VSEPR theory tells us each carbon is trigonal planar o VSEPR theory tells us each carbon is linear (2) Use VSEPR to predict electron-group geometry of central atom.
H H
S atom (6 V. E.) (3) Select the corresponding hybridization scheme from Table 11.1.
3d 3d 3d

3p 3p

3s P atom (5 V. E.) 3s
1 C-C σ-bond from direct (Electron group
overlap of sp hybrid orbitals % s-character geometry)

Sigma (σ) bond – direct orbital overlap Pi (π) bond – indirect orbital overlap 1/2=50%
1/3=33%
2 C-C π-bonds from 1/4=25%
Alternate picture showing indirect overlap of
1/5=20% Figure 11-14
orientation of two pi bonds unhybridized p orbitals
1/6=17% sp3d hybridization
15 (clearer than text image) 16 17 18

Example 1 Example 2
What is the hybridization at the central oxygen atom in O3 ? What is the hybridization at the central iodine atom in I3- ?
(1) Write Lewis structure (1) Write Lewis structure
Hybridization scheme can change in a reaction Review: Constructive & Destructive Interference of Waves
octet deficient normal octet 18 V.E.    22 V.E.   
O O O I I I





–
••
F
••
F      Expanded valence shell

••
••
••

••

•• – •• ••
B F B F (2) Use VSEPR to predict electron-group geometry. (2) Use VSEPR to predict electron-group geometry.
••
••

F
••
••

•• •• ••
••

•• F F ••
••

F
••
••
••

••

••
At the central O atom, it is AX2E, thus should be trigonal planar for At the central I atom, it is AX2E3, thus should be trigonal
Trigonal planar (sp2) Tetrahedral (sp3)
the electron group geometry and bent for the molecular geometry. bipyramidal (electron group geometry). Molecular geometry is
•• ••
F linear.
••
••

F H
••
••

Similarly, BF3 can Constructive interference occurs when Destructive interference occurs when
readily react •• - +
F B N H the troughs and crests are in phase, the troughs and crests are out of phase,
••

with NH3 B + NH3 ••

••

(3) Select the corresponding hybridization scheme. (3) Select the corresponding hybridization scheme. leading to addition of the two waves. leading to cancellation of the two waves.
••

•• F F ••
••

F H
••
••
••

••

••
21 For a trigonal planar electron group geometry, the hybridization is sp2. For trigonal bipyramidal, it is sp3d hybridization.

Recall that O3 is bent, but azide N3- is linear.

Wavefunctions can also be “in phase” or “out of phase”

Molecular Orbital (MO) Theory Construct and Label Mos of H2 MO and Potential Energy
• We have learned that atomic orbitals (AOs) are localized on atoms. Potential
+ + + bonding
orbital
y Mol = y 1 + y 2 wave 1 wave 2
High electron density between
nuclei promotes bond formation energy Potential energy curve for anti-bonding MO
- - - • In molecular orbital (MO) theory, we combine atomic orbitals to create + + σ 1s ψ2
new molecular orbitals that are localized differently. + + + + - σ 1s*
unstable
Angular Node
• The “signs” of AOs • Example: H2 1s 1s Origin of AOs wave 1 + wave 2
We can define two molecular Type of bond (constructive) attraction
(atomic wavefunctions)
have nothing to do with H H orbitals (MO) for H2 as:
electron spin and charge. + +
1s 1s y Mol = y 1 + y 2 antibonding E=0
y Mol = y 1 -y 2 High electron density in outer regions

y 1 (1s ) y 2 (1s )
orbital of nuclei favors bond dissociation
• They reflect the “phase” Atomic orbitals y Mol = y 1 -y 2 + - ψ2
relationship between σ 1s* +
different regions of the + - - + σ 1s Potential energy curve for bonding MO
“standing wave”. wave 1 - wave 2
• This is known as the linear combination of atomic orbitals (LCAO) 1s 1s One nodal plane (destructive) repulsion 0 re internuclear separation
approximation. So, the LCAO-MO theory.
(bond length at equilibrium)
 Basic Rules in MO Theory Diatomic Molecules in the 1st Period !"#
Diatomic Molecules in the 1st Period !"!
Molecular Orbitals – 2nd Period Elements
Bond Order = =1 Bond Order = !
=0
!
H2 – 2 e- + - He2 – 4 e- + -
• Each MO can be represented mathematically as a linear combination of AOs
Therefore a single bond in H2 This means that He2 cannot be formed!
• First period (row) elements use only 1s AOs.
• The total number of MOs is equal to the total number of AOs • Second period (row) elements have 2s and 2p AOs available.
• MOs can be classified as bonding, antibonding, or nonbonding • Overlap of two AOs of the s type produces a sigma bond (σ).
• The electron configuration for the molecule is obtained by placing electrons • Two types of overlap from AOs of the p type:
into the MOs according to their energies (from low to high) following

Energy

Energy
• End-to-end overlap – sigma bond (σ)
similar Hund’s rules.
1s 1s 1s 1s
• Side-to-side overlap – pi bond (π)
• Stable species have more electrons in bonding MOs than antibonding MOs.
However, He2 does exist where the two
He atoms are held together by van der
# of e− in bonding MOs − # of e− in antibonding MOs Waals force. This shows the limitation
Bond Order = + +
2 of the current MO theory.

AO MO AO AO MO AO

MOs from p Orbitals – σ Overlap MOs from p Orbitals – π Overlap How do we fill electrons? Let’s Take a Closer Look:
σ 2* pz σ 2* pz

wave 1 wave 2 Triply degenerate 2p AOs

wave 1 wave 2
* * * *
π π π π
+ + + + • Example: O2 2p
2 px 2 py
2p 2p
2 px 2 py
2p

- - - - • Recall that none of the previous π 2 px π 2 py π 2 px π 2 py

Destructive Interference
chemical bonding theories (Lewis and
Constructive Interference VB) can explain why O2 is paramagnetic. σ 2 pz σ 2 pz
• We have a total of 16 electrons for O2 doubly degenerate π and π* MOs
(core + valence electrons). We use the σ 2s* σ 2s*
same rules as adding electrons to the

Energy

Energy
2s 2s 2s 2s
wave 1 + wave 2 AOs.
(constructive) g
din
wave 1 – wave 2
(destructive)
on So O2 has unpaired electrons! σ 2s σ 2s
+ ing ti-b
nd An Electron configuration for O2 molecule,
- - Bo + +
One nodal plane (s1s)2(s1s*)2 (s2s)2 (s2s*)2 (s2pz)2 (p2p)4 (p2p*)2 σ 1s* σ 1s*
- - One nodal plane Two nodal planes 1s 1s 1s 1s
B. O. = (10 - 6)/2 = 2 (O2 has a double bond!)

y Mol = y 1 + y 2 y Mol = y 1 -y 2 Total # of e- in Total # of e- in

σ 1s σ 1s
bonding MOs antibonding MOs AO MO AO

Complication for Lighter Elements (Z ≤7) Orbital Energies Z=3 4 5 6 7 8 9 What about lone pairs? Delocalized Electrons (Delocalized MO)
Li2 Be2 B2 C2 N2 O2 F2
• Because σ2s and σ2p MOs occupy the same space (along the bond direction), they interact with each other • Bond order (# of bond
σ*

causing energy levels related to 2p to shift upwards (so-called 2s-2p mixing). σ 2* pz • Example: O3 Lewis structures
pairs) is determined by the
• This effect is more pronounced for light elements (Z≤7) because their 2s and 2p orbitals have smaller energy Can you σ 2* pz net number of valence 2px,y
π∗
2px,y
• Let’s just look at the
difference (see Figure 11-27). π 2* px π 2* py electrons in bonding and 2pz 2pz
calculate bond p orbitals
antibonding MOs. In F2,
σ 2* pz
Z≤7
σ 2* pz
Z>7 orders and σ 2 pz π 2* px π 2* py bond order = (8-6)/2 = 1
π
A total of 18 electrons
predict their (single bond). Trigonal-planar electron group (sp2)
* * magnetic Shifting due to • Lone pairs are made from σ 2 nodes
π 2* px π 2* py π π
2s-2p mixing
2 px 2 py
2p 2p 2p 2p property? all other valence electrons σ*
in bonding and
π 2 px π 2 py π 2 px π 2 py antibonding MOs that are 2s
See Figure 11-26
2s
σ 2 pz π 2 px π 2 py
canceled out. # of lone 1 node π bond order
σ 2 pz pairs = 12/2 =6. Lewis
Small ΔE σ 2 pz σ = (2 – 0)/2 = 1
π 2 px π 2 py Large ΔE structure for F2
* σ 2s* • Lewis theory: lone pairs
F F2 F
0.5 of π bond for
σ 2s* σ 2s σ 2s* are localized on atoms. 0 node each O-O bond
2s 2s 2s 2s σ 2s • MO theory: “lone pairs”
.. ..
σ 2s are shared by the whole :F:F:
.. .. 3 unhybridized 2p AOs
σ 2s σ1s and σ1s* (each having 2 core electrons) are not shown for clarity molecule.
σ 2s

Example 1
The following data show that, removing an electron from N2 forms an ion with a
MO Theory & Benzene (Delocalized Electrons) Phenolphthalein Extended π Systems weaker, longer bond than in the parent molecules, whereas the ion formed from
MO theory can be used to explain the color of compounds with conjugated π system. O2 has a stronger, shorter bond. Can you explain these trends?
π bond order = (6 – 0)/2 = 3
N2 N2+ O2 O 2+
Most organic π electrons
MOs show that π
compounds are Bond energy (kJ/mol) 945 841 498 623
electrons are
colorless, because the
delocalized within the HOMO-LUMO gap is in
Bond length (pm) 110 112 121 112
LUMO=Lowest Unoccupied MO
molecule (shared the UV region. Bond order
among all 6 carbons). However, when the
nonbonding
HOMO=Highest Occupied MO 3 2.5 2 2.5
sp
3
sp
2
extended π system is (# of bone pairs)
large enough, this gap
can be decreased to
visible, giving rise to
color of compound.
Benzene resonance Extended π
Absorption of these
structures
system photons is responsible ….
for the colors that we
see. Figure 11-35) Formation of π MO in a long-chain polyene.
Figure 11-30) Bonding from VB method

N2 (10 V. E.) O2 (12 V. E.)

18
Intermolecular Forces: Bigger Picture Questions Consequences of Intermolecular Forces Boiling Point Trends for Halocarbons Van der Waals Forces
400

Important • Earlier we have seen that at high pressures and low I • van der Waals forces: All intermolecular forces cause the non-ideal behavior of gases (van
temperatures intermolecular forces cause gas der Waals equation from Ch. 6)
properties/applications:
300

behavior to depart from ideality • Molecular properties such as dipole moment and polarizability are important physical
• Superhydrophobic, Hydrophobic, • When these forces are sufficiently strong, a gas 200 Br bases for attractive intermolecular forces.
Hydrophilic Surfaces and Coatings condenses to a liquid - are governed by the distribution of electron density within a molecule, size, and

Boiling Point (⁰C)

electronegativity of atoms in molecules
Cl
100
• Chemical Separations (e.g., Gas • Intermolecular forces keep molecules in such close
Chromatography, Azeotropes, proximity that a liquid has a certain density at a
Distillation) given pressure and temperature. 0

• Protein and DNA structure, -100

replication F
-200
• Drug/Protein Interactions,
Molecular shape
CH4 CH3X CH2X2 CHX3 CX 4
Electrostatic potential maps in methanol and ethanol
Petrucci, Figure 6-20 What causes the differences in BPs and their trends for different halocarbons?

Polarizability Dipole Moment and Polarizability Dipole-Dipole Interactions Permanent dipoles

Dipole-Induced Dipole Interactions
• Interaction between a pair of polar attract each other
• The Polarizability of an atom is a measure of the extent to which its electron molecules that have a permanent dipole (positive to negative), • Dipole-induced dipole interactions can increase interaction of two molecules as the dipole
• A dipole moment (µ) is produced in a molecule
cloud can be distorted by external perturbations (externally applied electric when bond dipoles within the molecule do not • Molecules line up with a positive end of one
also called head-to- moment on one molecule can induce a dipole in another non-polar molecule.
field, the approach of another atom, molecule, or ion, etc.). tail interactions
cancel out. molecule aligned with the negative end of • Note: ion can also induce dipole, produce similar
• Polarizability increases with the size of the atom. • Can examine and sum bond dipoles (magnitude and another molecule ion-induced dipole interaction
direction) to determine a net molecular dipole.
• Relatively strong
• Polarizability (a) of a molecule measures how Petrucci, Figure 10-16, page 448
easily the electron cloud can be perturbed from
Electrostatic
its “average” shape. attraction
Parallel between polarizability of an
• Note: unit of polarizability is same as volume
atom ( ) and atomic volume (------). • The perturbation can be caused by the approach of an
ion, a molecular dipole, or the application of an electric
field.

Petrucci, Figure 9.18 Boiling point: −127.8 °C Boiling point: −82.1 °C

Some Properties of Selected Nonpolar Compounds Boiling points of some hydrides of the elements of groups 14, 15, 16, and
London Dispersion Forces 17
Hydrogen Bonding
Melting and Boiling Points of Halogens
In a hydrogen bond an H atom is covalently bound to a
Physical State at
• London dispersion forces are attractive forces, even between non-polar molecules Total Number of highly electronegative atom (e.g., F, O, N, Cl, Br)
Molecule Melting Point (°C) Boiling Point (°C) Room
Electrons
• Begins with a temporary dipole (also called an instantaneous dipole) caused by random Temperature
shift of electron density to one side of a non-polar molecule or atom, depends on F2 18 −220 −188 gas
polarizability Cl2 34 −102 −34 gas
• Instantaneous dipole can induce a dipole in another non-polar molecule or atom. This is Br2 70 −7 59 liquid
called an instantaneous dipole-induced dipole interaction I2 106 114 184 solid

• London dispersion forces are relatively weak

• More polarizable non-polar molecules generally have higher boiling points Another trend: More
electrons results in In gaseous HF many of
greater polarizability, the molecules are
stronger London Chapter 12, Figure 12-5 arranged into cyclic
dispersion forces (HF)6 structures
The values for NH3, H2O, and HF are unusually high compared with those of other
Hydrogen Fluoride (HF)
members of their groups. Why?

Hydrogen Bonding in Water Boiling Point Trends - assessment

Hydrogen Bonding c) Water is less dense in its solid form than its liquid.
(a)Each water molecule is linked to four others - weak hydrogen bonds between liquid water
through hydrogen bonds. The arrangement is molecules constantly form and break, so the
• H atom is covalently bonded tetrahedral. Each H atom is situated along a line
to a highly electronegative molecules are randomly distributed;
joining two O atoms, but closer to one O atom
atom (typically F, O, or N) - when water freezes, the bonds form rigid lattices
(100 pm) than to the other (180 pm).
with each water molecule bonded to four others. Science Media Group

(b)For the crystal structure of ice, H atoms lie between These lattices contain relatively large gaps, which
• In these examples of pairs of O atoms, closer to one O atom than to the would be filled with atoms if the water were liquid.
hydrogen bonding, we have other. (Molecules behind the plane of the page are
B.P. −162 °C B.P. −89 °C B.P. 36 °C
the bond between two light blue.) O atoms are arranged in bent hexagonal
separate molecules, which is rings arranged in layers. This characteristic pattern is d) In liquid phase, water molecules have hydrogen
termed intermolecular similar to the hexagonal shapes of most snowflakes. bonds only to some of their neighbors. Water
Hydrogen Bonding. molecules pack ~ 10% more densely in the liquid
than in the solid. ethanol butane CS2 ethylene glycol
Snowflakes B.P. 78 °C B.P. −1 °C B.P. 46 °C B.P. 197 °C
2 3 4
Short video discussing at least 17 forms of ice More on this later…
 H-Bonding: important for so many molecules… life Other properties affected by H-Bonding Summary of Non-Covalent Interactions: Table 12.3 Summary of Non-Covalent Interactions: Table 12.3 cont.
• Hydrogen bonds hold complementary strands of DNA together
Viscosity • The viscosity of a liquid can also be related to the intermolecular
forces and to molar mass
• Higher molar mass means more viscous - higher “centipoise” (cP) 1 P = 0.1 Pa.s
= 0.1 N.s.m−2
• Stronger intermolecular forces mean more viscous liquids since
the molecules are “less free”
• Glycerol C3H8O3 has three OH groups and therefore lots of
DNA hydrogen bonding
Nucleotides pair precisely based on the position of
an available hydrogen bond.
- Thymine has one donor and one acceptor site
that pairs perfectly with the nucleotide adenine's
complementary acceptor and donor site.
- Cytosine pairs perfectly with guanine through
three hydrogen bonds.
A:T G:C
One hydroxyl Two hydroxyls Three hydroxyls
[Link] 5 6 7 8
Petrucci, Chapter 12, Page 524 Table 12.3, p.527 Table 12.3, p.527

Properties of Liquids- Surface Tension Consequences of Surface Tension Consequences of Surface Tension
12-2 Some Properties of Liquids
Surface Wetting-high energy and low energy surfaces
• Surface tension is caused by molecular attractions -examine wetting behaviour of a surface by a droplet
Cohesive Forces • Interior molecules have more neighbors and experience more attractive
Intermolecular forces between like molecules. intermolecular interactions than surface molecules
Adhesive Forces • Liquids tend to exhibit minimum surface area (i.e., a spherical shape)
Intermolecular forces between unlike molecules.
• The surface behaves as if it were tightened into an elastic film Steel is much denser than water, however, the paper
Surface Tension clip can be supported by water surface tension
Energy or work required to increase the surface
area of a liquid. Strong intermolecular forces can lead to high
surface tension

Surface tension is the energy needed to increase A man sits on a vat of mercury. The surface tension
the surface area of a liquid. Units of J m-2. of water is 7.28 x10-2 J m-2 while that of mercury is
more than six times larger at 47.2 x10-2 J m-2
FIGURE 12-10 Droplets on wax, 100o
An effect of surface tension illustrated Why do you think mercury has contact angle Superhydrophobic Colocasia
20 µL droplet of water on superhydrophobic
The potential energy of the ‘water strider’ as it sinks (from its such a high surface tension? surface, <1o sliding angle (SA) “elephant ear” Plant
9 10 mass) is balanced by the energy increase of increasing the 11 12
water surface area where the feet ‘dent’ the surface Why would plants evolve this type of surface?

Surface Wetting with Water Phase Changes Enthalpy of Vaporization Enthalpy of Vaporization
Hydrophobic or Hydrophilic? [Link]

Hydrophilic
Liquid-Vapour: getting to equilibrium
Glass Conditions for vaporization: changing the equilibrium
[Link]
a) Starting with liquid phase only, liquid
molecules move and collide, have a • Increased Temperature – more molecules have
distribution of kinetic energy sufficient KE to overcome intermolecular forces
Polydimethylsiloxane Hydrophobic
[Link] - Some liquid molecules with high kinetic (P* increases with higher T)
Lab Chip, 2014, 14, 1564-1571
energy reach surface, have enough energy • Reduced strength of intermolecular forces
to leave the liquid surface - lower KE needed to overcome intermolecular forces
Hydrophilic
Amine Modified Surface b) Gas-phase pressure increases, gas molecules move and collide, have a
Applied Surface Science 300:22–28, 2014 distribution of kinetic energy
- Some gas molecules with low kinetic energy collide with the surface • What about Increased Surface area?
Hydrophobic
and lose enough energy to return to the liquid phase. - greater number/proportion of molecules at the surface
Polytetrafluoroethylene
(Teflon)
- increases rate of phase change towards equilibrium but does not change the
c) Equilibrium: equal rates of evaporation and condensation occur when proportion of liquid and gas at equilibrium in a closed system
Pressure = Vapour Pressure of the liquid.
Energy transfer is required for every phase change - Vapour pressure at equilibrium = P*
What kinds of intramolecular forces are involved? 13

Enthalpy of Vaporization Enthalpy of Vaporization Intermolecular Forces and Enthalpy of Vaporization Boiling
Boiling point, Tb = Temp at which P* = Patm
Figure 6.16, Page 220 • Definition of volatility?
Why does remaining liquid feel cool during evaporation? • In order to actually boil (make bubbles) T must
• Liquids with “appreciable” vapor pressure at room temperature are often called
be slightly higher than Tb so that P* > Patm
• The higher KE molecules in the liquid are lost through “volatile”, while those with low vapor pressure are called “non-volatile”.
evaporation
• This definition is arbitrary. There’s no universally accepted definition. It’s better to • Gas molecules are far apart, so intermolecular
• The average kinetic energy of the remaining liquid talk about liquids being more or less volatile by comparison. forces are now mostly eliminated.
molecules decreases
• From the Petrucci text, p. 532
• Liquids with higher intermolecular forces will
• Liquid will cool and draw heat from surroundings as Enthalpy of Vaporization (DvapH) - the quantity of heat that must be absorbed to vaporize
"! have higher boiling points (if all else remains
evaporation continues & # %&!
one mole of liquid at constant temperature and pressure
! " = 4% "# * $ #'( constant).
2%()
• The quantity of heat required to vaporize one mole of Enthalpy of Condensation (DcondH) - the quantity of heat that will be released to condense
liquid at constant temperature and constant pressure is Maxwell-Boltzmann Distribution
one mole of gas at constant temperature and pressure • Normal boiling point refers to boiling point at
called enthalpy of vaporization ΔvapH Liquid phase has similar 1 atm = 760 mm Hg = 101.325 kPa
distribution of kinetic energies DvapH is an endothermic process so is always positive, conversely DcondH is always negative.
DvapH = -DcondH
 Vapour Pressure and Boling Point Clausius-Clapeyron Equation Example 1: Calculation of Vapor Pressure of Water with the C.C. Equation
Example
Example 2: Theboiling
2: The normal normal
pointboiling point of
of nitrobenzene nitrobenzene
is 210.9 is
oC. If the vapour

• Boiling occurs in open containers 210.9

pressure oC. oIf
at 180 C isthe vapor
353.2 pressure
mm Hg, atvapour
what is the 180 opressure
C is 353.2
at 200 mmoC? Hg,
What is the vapour pressure (in atm) of water at 20°C?
(const. Pext)
#! − ∆#$% ( 1 1 ln
(!
=
− ∆#$% - 1 1
( − ) what is the vapor pressure at 200 oC? ln
#$ (! − ∆*+,
ln = =
−∆ -#$%1- 11 1
( −( − ) )
(" . 1! 1" #% (" . . 1$ 11!% 1"
• Lower pressures result in lower boiling ln = ( − ) DvapH = 44.0 kJ/mol
point #" ) ,! ," P1= 760 T1= 210.9 + 273.15 = 484.05
P2= 353.2 T2= 180 + 273.15 = 453.15
From definition of normal boiling point (Temp at which Vapour pressure = 1 atm) .
– A consequence is different cooking times at
Can set P1 = 1 atm and T1 = 373.15 K. T2 = 293.15 K Convert 44.0 kJ/mol to 44 000 J/mol 565. 8 − ∆ <=>? A A
different altitudes. P1, P2 in any units 34
9:;. ;
= ( −
@. 5AB6 B65. A6 B@B. ;6
)

• When T > Tb (const. Pext), substance T in Kelvin -0.7663 = -delH 0.00014

exists solely as a gas (vapour) at ∆#$% ( in J/mol ln
(!
=
− 44 000 9:;<&" 1
−
1
= −5292 ? D 0.000732 ? &"
8.3145
equilibrium R = 8.314 J/molK 1.00 atm 8.314 9:;<&" ? &" 293 ? 373 ? -delH = -45227
delH = 45.23 kJ
• When T ≤ Tb (const. Pext), can have
liquid and vapor at equilibrium Ln(P2) = -3.874 + ln(1.00) = -3.874 P1= 353.2 T1= 180 + 273.15 = 453.15
P2= ??? T2= 200 + 273.15 = 473.15
• Describes the observed relationship between the vapour pressure of a gas above a liquid #2 − B6889 A A
Chapter 12, Figure 12.18, Page 533 P2 = exp(-3.874) = 0.0208 = 0.021 atm Note: for T2 = 0°C = 273 K, get P2= 0.0055 atm
and the temperature of that system. 34
565. 8
= ( −
@. 5AB6 B95. A6 B65. A6
)

Vapour pressure curves of several liquids • If values for ΔvapH and one pair of T and P known, can calculate P at alternate T ln(P2) - ln(353.2) = -5439.9 x -9.32801E-05
(a) Diethyl ether, (CH3CH2)2O; (b) benzene, C6H6; (c) water, H2O; (d) toluene, C6H5CH3; (or T at alternate P) ln(P2) - 5.86703 = 0.507434063
(e) aniline, C6H5NH2; The normal boiling points are the temperatures at the intersection of
the dashed line at P = 760 mmHg with the vapor pressure curves.
• For P=101.3 kPa, T = Tb (one pair of values if Tb is known) Ln(P2) = 6.374468532
P2 = 586.7 mm Hg

Phase Changes Critical Point: deviation from normal phase behaviour Critical Point: deviation from normal phase behaviour Melting, Melting Point and “Enthalpy of Fusion”
• As a crystalline solid is heated, its atoms, ions or molecules Heat added at
• Phase changes involve an exchange of energy begin to vibrate more vigorously
constant rate
• If a liquid is heated in a closed container • Critical point: the point where liquid and
• Apply heat to a material at a constant rate. • Mainly affected by ‘unpacking’ of the structure of the solid
– Density of a liquid decreases as vapour become indistinguishable. The
As it reaches a phase change, temperature • Energy Change is largely due to “packing energy”
temperature is increased temperature is called the critical temperature
remains constant even though heat is still TC and the pressure is denoted PC • Quantity of heat required to melt a solid at constant pressure
being removed or applied. – Density of vapour phase increases as more is the enthalpy of fusion DfusH, a property of a substance
molecules are vaporized
• Why? • The critical point is the highest point on a Note: for phase changes, “fusion” means “melting”, and we still use the
– Eventually the densities of vapour and phrase “ethalpy of fusion” instead of “enthalpy of melting”
liquid phases become equal vapour pressure curve and represents the
Chapter 12, Figure 12.23, Page 540

• The surface tension of the liquid approaches highest temperature at which a liquid can
zero and the interface between vapour and exist.
At the temperature of the phase change (e.g. boiling point of water), energy is liquid disappears
consumed by the endothermic phase change process. As a result, the temperature
remains constant even while heat is absorbed until the liquid is boiled away.
More on this in the next lecture.

Sublimation and Deposition Sublimation and Deposition Bringing it all together: Phase Diagrams Bringing it all together: Phase diagrams
Phase Diagram Showing different physical processes/transitions
• The direct passage of molecules from the solid to the vapour state and the • At the sublimation point, sublimation is equivalent to melting followed by
vapour to the solid state are called sublimation and deposition respectively. vaporization Graphical representation of As we add or remove energy,
• The enthalpy of sublimation DsubH is the quantity of heat needed to convert a • i.e. DsubH = DfusH + DvapH the conditions of temperature intermolecular forces weaken or
solid to vapour and pressure at which solids, strengthen and phase is changed.
liquids and gases exist.
• You can therefore replace DvapH in the Classius-Clapeyron equation with DsubH
to calculate sublimation pressure in a temperature and pressure range where
Each dot is colour-coded for Two points, T and C are also important.
a solid sublimes T ≡ Triple point, where three phases
the phase at that temperature- co-exist in equilibrium.
pressure combination C ≡ Critical point where gas and
liquid become indistinguishable.

Sublimation of CO2 Sublimation and Deposition of I2 Deposition of H2O

Normal Freezing Point (NFP) and Normal Boiling Point (NBP) are where the P=1 atm
Red- solid is stable; Blue- liquid is stable; Brown- gas is stable dashed line intersects the melting and vaporizing pressure-temperature curves.
Sublimation of CO2 Sublimation and Deposition of I2 Deposition of H2O

Phase Diagrams Phase Diagrams: pure compounds at each phase Phase Diagram for Iodine Phase Diagram for Carbon Dioxide
• Lines represent equilibrium between two phases
There are two empirical rules which are somewhat O - Triple Point
interesting. For 1 mole of most substances, the ratio O - Triple Point C - Critical Point
Pc Vc C - Critical Point O-C - Vapour Pressure Curve
=.25 to .35 O-C - Vapour Pressure Curve O-B - Sublimation Curve
RTc
O-B - Sublimation Curve O-D - Melting (Fusion) Curve
Normal
whereas for an ideal gas it is 1 (obviously, critical fluids Melting O-D - Melting (Fusion) Curve
Normal Note: The triple point is greater
do not behave much like ideal gases). 1 atm
Point Boiling than 1 atm. A line at P=1 intersects
The ratio of boiling point to critical temperature is also Point the sublimation curve
consistent among many substances When CO2 is heated in an open
container at 1 atm, it sublimes
Tb away (i.e. It does not melt!)
= 0.58 to .65 Tb
Tc

Pc, Vc and Tc are the critical pressure, volume and temperature (in K)
of a substance, respectively. Tb is the “normal” boiling point.
SCF link: [Link]
 Supercritical Fluid Carbon Dioxide Supercritical Fluids- Safer Solvents for Industrial Processes Phase Diagram of Water (extended) Crystalline Solids
Decaffeination of Coffee
Phase diagram for water
Supercritical Fluids have a number
of applications: Triple point O is at 0.0098 °C and 0.0060 Crystalline
atm. (The normal melting point is at exactly Solid
• “Green” Solvent to carry out
0 °C and 1 atm)
chemical reactions
• Supercritical fluid Critical point C is at 374.1 °C and 218.2
chromatography atm. At point D the temperature is -22.0 °C Network
caffeine Metallic Molecular
and the pressure is 2045 atm. Covalent Ionic Solid
• Industrial extraction processes Solid Solid
Solid
(e.g. decaffeination of coffee) • Dichloromethane (CH2Cl2) and ethyl acetate (CH3CO2C2H5) are effective solvents for
caffeine extraction, but remove some flavour and aroma components. Both solvents
The phase diagram of water shows that it is
are toxic and residual solvent can remain in the decaffeinated coffee. polymorphic (i.e. it can exist as a solid in
• Supercritical fluid extraction using carbon dioxide is now being used as a more more than one form) Nonpolar Polar H-bonded
effective and environmentally friendly decaffeination method.
• Removes 97−99% of the caffeine, leaving more of coffee’s flavour and aroma
compounds intact. Because CO2 is a gas under standard conditions, it can be easily
removed and the caffeine recovered 2

Network Covalent Solids Ionic Solids Metallic Solids

Covalent bonds extend throughout a crystalline solid and the entire crystal is held together by Ionic bonds extend throughout a crystalline solid. Hard, moderate to very high melting points,
strong forces. Most are very hard, most are not conductive, and most sublime or melt at high non-conductors as solids, but good electric conductors as liquids. Many are soluble in polar Metallic bonds extend throughout a solid, may be a crystalline solid
temperatures. solvents. e.g., NaCl, NaNO3, MgO
q Bonding described as a network of
Diamond positive ions immersed in a sea of
electrons.
Graphite
q Very good conductors of electricity
stemming from delocalized electrons.

q Metallic bonding forces are strong; thus,

metals generally have high melting points
e.g., Al, Fe, W, Cu, Sn
Fullerene,
like ionic solids
a.k.a. “Buckyball”

Carbon Nanotube 3 4 Copyright © 2017 Pearson Canada Inc. 6

Molecular Solids 12-5 Nature of Bonding in Solids: Summary Crystal Structures Seven Crystal Systems
q Made up of discrete molecules that • Solid structures that have plane surfaces, sharp edges, and regular geometric shapes.
interact via weaker intermolecular • Crystals with regular macroscopic structure have an underlying regular arrangement of
forces atoms, ions or molecules.
Lattice
q Soft, extremely low to moderate a regularly repeating geometric array of points.
melting points, soluble in some Space lattice
nonpolar solvents a regularly repeating arrangement of points in 3D.
Crystal structure
q Noble gases form solids at low a regularly repeating geometric array of spheres for
temperature, held together with crystalline solids.
e.g., He, I2, CO2, CH4
London Dispersion Forces. Described Unit cell
with the “molecular” solids even if A small portion of the lattice which is representative of
composed of isolated atoms. the lattice as a whole. It can be systematically
FIGURE 12-37
translated through space to create the entire solid.
The Cubic Lattice We will focus on the Cubic crystal system in this course.
7 8 9 10

Unit cells in the cubic crystal system Closest packing of spheres Closest packed structures The Holes (or Voids) in Closest Packed Structures
The three-dimensional lattice is arranged so that the centers of the structural
When spheres are stacked together there must always be some unfilled space.
particles (atoms, molecules, ions) of the crystal are situated at lattice points
Trigonal Hole - Formed by three
Arrangements that place the spheres in as close contact as possible with the spheres in one of the layers
ABC volume of the holes at a minimum are known as closest packed structures

Tetrahedral Hole - Formed when

Model a sphere sits in the dimple of the
showing lower layer
cubic
closest
ABAB packing
Octahedral Hole - Formed between
Note: Three different layers two groups of three spheres.
until pattern repeats
11 13 14 15
Closest Packed Structures Cubic closest-packed (CCP) = Face-centered cubic (FCC) Hexagonal cubic closest packing (HCP) of spheres Coordination Number of Spheres/Atoms in Crystal
Two possibilities depending on the placement of packing of spheres
the third layer of spheres The number of atoms with which a given atom is in contact with is called the
A Hexagonal “cutaway” coordination number
of HCP spheres.
A
HCP (note repeat portion
B
C FCC in red corresponding
to thicker grey lines
B A
opposite)
A
Hexagonal packed
Select portions of CCP Rotation shows FCC
layers with vertical
layers – still have arrangement of In FCC closest-packed structure, In HCP closest-packed structure, holes also
A, B, A pattern
vertical A, B, C, A packed spheres at a holes account for 25.96% of the account for 25.96% of the total volume
(note thicker grey
pattern different angle total volume - the packing is - the packing is also “~74% efficient”
linking lines) For the HCP and CCP (incl. FCC) closest-packed
In this arrangement the holes account for “~74% efficient” structures the coordination number is 12
25.96% of the total volume 16 2 3 4
Or “face-centred cubic (FCC)”

Crystal packing and the “unit cell” Multiple unit cells pack to make a bulk crystal Portions of sphere in a cubic unit cell Portions of sphere in a hexagonal unit cell
A unit cell is the smallest repeating unit that can be stacked in 3-dimensions to
How spheres are shared among unit cells How spheres are shared among unit cells, number of spheres per unit cell
form the bulk material
1/6 sphere

Body-centered cubic unit cell

Note how unit cells 1/12 sphere
contribute portions of
spheres at the corners 4x1/6 + 4x1/12 + 2/3 + 1/3
to combine into 1/3 sphere
= 2 spheres
complete spheres in
the bulk material 1 sphere ½ sphere ¼ sphere 1/8 sphere 2/3 sphere

Outside lines of unit cell cube There is a full sphere in the

intersect at center of corner center and 1/8 of a sphere at sphere in center sphere in face sphere on edge sphere at corner
spheres – 1/8 of each corner each of 8 corners: a total of
sphere is inside the unit cell 2 spheres are in the unit cell Note: this HCP figure is 3 unit cells
5 6 7 8

Portions of sphere in cubic unit cells Portions of sphere in cubic unit cells Empirical formula from the unit cell Empirical formula from the unit cell
Number of spheres per unit cell for various packing patterns Number of spheres per unit cell for various packing patterns
- A sphere could represent a molecule (e.g. solid CH4) or an atom (e.g. solid Xe) Below is the unit cell of cesium chloride. What’s the empirical formula? Below is the unit cell of Rutile. What’s the empirical formula?

(or Atoms) (or Atoms) (or Atoms)

Cl− Ti4+

Cs+ = 1
Ti4+ = 1 + (8 x 1/8) = 2
Cl− = 8 x 1/8 = 1
Cs+ O2− O2− = 2 + (4 x ½) = 4
Empirical formula = CsCl
Empirical formula = TiO2

Atoms/unit cell 1+ 8 x 1/8 = 2 6x 1/2+ 8 x 1/8 = 4 8 x 1/8 = 1

9 10 11 12

Video with animation showing packing and Ionic Crystal Structures Ionic Crystal Structures Ionic Crystal Structures
examples of unit cells and coordination number Consider an ionic crystal formed by first packing the anions. The size of the holes is related to
• Apply the “packing of spheres” model to an ionic crystal Given various holes in a closest-packed array of anions, which holes do the cations occupy?
the radius, R, of the anions used to form the structure
• have positively charged (cation) and negatively charged (anion) spheres • Cations are placed into holes that are slightly smaller than the cation
• the cations and anions are usually different sizes (anions are generally larger) The radius of the holes, r, can be found using the Pythagorean formula as follows: • Anions are pushed apart by the cation (reducing repulsion), while
[Link] • Oppositely charged ions are in close proximity anions and cations are in direct contact (maximizing attraction)
- Packing in cubic cells – they call spheres “particles” • Assume closely packed arrangement of ions of one type (usually anions),
holes filled by the opposite charge ions a 2 + b2 = c 2
• The relative cation and anion sizes are important in determining the particular packing arrangement Cation in tetrahedral hole: bigger than tetrahedral
(2R)2 + (2R)2 = (2R+2r)2 but smaller than octahedral hole
2√2 R= 2R + 2r
(2√2- 2)R = 2r 0.225 < ( rcation/Ranion) < 0.414
(√2-1)R = r
r = 0.414 R Cation in octahedral hole: bigger than octahedral
Cross section of an octahedral hole but smaller than cubic hole

0.414 < ( rcation/Ranion) < 0.732

Trigonal hole: r = 0.155·R Cation in cubic hole: bigger than cubic hole
Tetrahedral hole: r = 0.225·R
Note: this HCP figure is 3 unit cells FCC unit cell Octahedral hole: r = 0. 0.414·R 0.732< ( rcation/Ranion)
Holes in face-centered cubic unit cell Cubic hole: r = 0.732·R
13
 Atoms in unit cell
Trigonal hole: r = 0.155·R
Tetrahedral hole: r = 0.225·R Looking at CsCl Trigonal hole: r = 0.155·R
Tetrahedral hole: r = 0.225·R Some More Complex Unit Cells X-Ray Diffraction
Octahedral hole: r = 0. 0.414·R Octahedral hole: r = 0. 0.414·R
Example: NaCl Cubic hole: r = 0.732·R Cubic hole: r = 0.732·R
• A unit cell is defined such that:
This ratio says Na+ ions will occupy Cs+ This ratio saysCs+ ions will occupy cubic holes
• Translation and repeating in 3D
octahedral holes in a cubic closest- Cl- with anions in a simple cubic structure Half of the tetrahedral
generates the entire crystal
packed array of Cl- ions holes are filled
• It is consistent with the formula of
the compound Total number of Cl- ions in the unit cell = (8 x 1/8) = 1 1:1 corresponding to
• It has the correct coordination Total number of Cs+ ions in the unit cell = (1X1) = 1 the formula CsCl Add Cs+ ion to
Total number of Cl- ions in the unit cell = (8 x 1/8) + (6x ½) = 4 cubic hole in Cl-
numbers of the ions Total number of Na+ ions in the unit cell = (12 x ¼) + (1X1) = 4 cubic crystal
C.N. Ca2+ = 8
F- = 4
simple cubic
unit cell
4:4 = 1:1 corresponding to
the formula NaCl
C.N. Ti4+ = 6
Coordination number for Na+
ions = 6
O2- = 3

The cesium chloride unit cell Coordination number for Cs+ ions = 8
The sodium chloride unit cell The coordination number is the number of nearest For substances with formulae MX2 or M2X the crystal structures are more complex,
neighbour ions of opposite charge that contact an ion Diffraction of X-rays by a crystal
cations and anions can have different coordination numbers (C.N.)

X-Ray Diffraction X-Ray Diffraction X-ray crystallography for very complex molecules to deduce structure X-ray Crystallography for very complex molecules to deduce structure
• To see how atoms are arranged in a crystal a short wavelength radiation is used
• X-rays encounter atoms and are scattered in all directions.
• The pattern of scattering is related to the distribution of electronic charge in
the atoms and/or molecules.
• The scattering is recorded by a photographic film or light sensitive detector.
• The pattern can be used to infer the crystal structure of the material

Wave a and b travel

different distances

The additional
distance is = 2d sin Θ

M. F. Perutz, Science, Vol. 140, No. 3569 (May 24, 1963), pp. 863-869
Hemoglobin: showing four protein subunits
Dr. Gabriele Schatte Photograph 51. and heme groups which bind oxygen
This x-ray crystallographic image taken by Dr. Rosalind Franklin
X-Ray diffractometer, Chernoff Hall, nλ= 2d sin Θ helped lead to the discovery of the DNA double helix by
Queen’s University Watson and Crick. The data also ignited a scientific controversy. • Not all proteins can be “recrystallized”, but when they can, X-ray crystallography can provide
© Hriday Bhattacharjee
X-ray diffraction [Link] extremely precise structures to help understand protein structure and function.
pattern for NaCl 1.5020051&id=images/medium/[Link].highlight_f1.jpg

P E R I O D I C T A B L E
Group
1
Atomic Properties of the Elements 18
IA FREQUENTLY USED FUNDAMENTAL PHYSICAL CONSTANTS §
VIIIA
1 2
S1/2 1 second = 9 192 631 770 periods of radiation corresponding to the Physical Measurement Laboratory [Link]/pml 2 1
S0

1
H speed of light
transition between the two hyperfine levels of the ground state of 133Cs
in vacuum
−1
(exact) §
For the most accurate
Standard Reference Data [Link]/srd He
cc 299 792
792 458
458 m m ss −34
−1
Hydrogen speed of light in vacuum 299 (exact) Helium
Planck constant
−1
6.626 070 15 x 10 −34J Hz −1 (exact) values of these and
1.008 Planck constant hh 6.626 070 15 x 10 −19J Hz 4.0026
1s
2 elementary charge e 1.602 176 634 x 10 −19C (exact) other constants, visit 13 14 15 16 17 1s
2
elementary charge e 1.602 176 634 x 10 C−1 [Link]/constants.
13.5984 IIA Avogadro constant
electron energy mNeAc
2 6.022 998
0.510 140 76
950x 10
23
MeVmol (exact) IIIA IVA VA VIA VIIA 24.5874
3 2
S1/2 4 1
S0 Boltzmann
proton mass constant mkp 1.672 649 xx 10
1.380 622
−23
10 Jkg
−27 K
−1 (exact) 5 2
P°1/2 6 3
P0 7 4
°
S3/2 8 3
P2 9 2
°
P3/2 10 1
S0
-19 (exact) Solids
2
Li Be electron voltconstant
fine-structure
electron
Rydberg mass
constant
eV
Rme 2
1.602 176 634
1/137.035
10
999 x 10
973 731.569 m
−31
9.109 383 70 x 10 −1kg
J
Liquids
B C N O F Ne
Lithium Beryllium energy equivalent m c 0.510 998 950 MeV15 Boron Carbon Nitrogen Oxygen Fluorine Neon
6.94 9.0122 R ec 3.289 841 960 x 10−27 Hz Gases 10.81 12.011 14.007 15.999 18.998 20.180
proton mass mp 1.672 621 924 x 10 kg 2 2 2 2 2 2 2 3 2 2 4 2 2 5 2 2 6
2 2 2 Rm hc 13.605 693 eV
1s 2s 1s 2s 2 1s 2s 2p 1s 2s 2p 1s 2s 2p 1s 2s 2p 1s 2s 2p 1s 2s 2p
5.3917 9.3227 electron
energy equivalent
volt eV
pc 938.272 088 MeV
1.602 177 999
-19
x 10 J Artificially 8.2980 11.2603 14.5341 13.6181 17.4228 21.5645
fine-structure constant 1/137.035 −23 −1 Prepared
11 2
S1/2 12 1
S0 Boltzmann
Rydberg constant
energy
molar gas constant
k
R hc
1.380
13.60565 x 10
693 1230
8.314 5 J mol
JK
−1 eV
−1 13 2
°
P1/2 14 3
P0 15 4
°
S3/2 16 3
P2 17 2
°
P3/2 18 1
S0
R 3K −1 −2

Na Mg Al Si P S Cl Ar
−11
Newtonian constant of G 6.674 x 10 m kg s
gravitation
3 Sodium Magnesium Aluminum Silicon Phosphorus Sulfur Chlorine Argon
22.990 24.305
2
3 4 5 6 7 8 9 10 11 12 26.982
2
28.085
2 2
30.974
2 3
32.06
2 4
35.45
2 5
39.948
2 6
[Ne]3s [Ne]3s [Ne]3s 3p [Ne]3s 3p [Ne]3s 3p [Ne]3s 3p [Ne]3s 3p [Ne]3s 3p
5.1391 7.6462 IIIB IVB VB VIB VIIB VIII IB IIB 5.9858 8.1517 10.4867 10.3600 12.9676 15.7596
Period

19 2
S1/2 20 1
S0 21 2D3/2 22 3F2 23 4F3/2 24 7S3 25 6S5/2 26 5D4 27 4F9/2 28 3F4 29 2S1/2 30 1S0 31 2P1/2 ° 32 3
P0 33 4S3/2 ° 34 3
P2 35
2
° 36
P3/2 1
S0

4
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
39.098 40.078 44.956 47.867 50.942 51.996 54.938 55.845 58.933 58.693 63.546 65.38 69.723 72.630 74.922 78.971 79.904 83.798
2 2 2 2 3 2 5 5 2 6 2 7 2 8 2 10 10 2 10 2 10 2 2 10 2 3 10 2 4 10 2 5 10 2 6
[Ar]4s [Ar]4s [Ar]3d4s [Ar]3d 4s [Ar]3d 4s [Ar]3d 4s [Ar]3d 4s [Ar]3d 4s [Ar]3d 4s [Ar]3d 4s [Ar]3d 4s [Ar]3d 4s [Ar]3d 4s 4p [Ar]3d 4s 4p [Ar]3d 4s 4p [Ar]3d 4s 4p [Ar]3d 4s 4p [Ar]3d 4s 4p
4.3407 6.1132 6.5615 6.8281 6.7462 6.7665 7.4340 7.9025 7.8810 7.6399 7.7264 9.3942 5.9993 7.8994 9.7886 9.7524 11.8138 13.9996
37 2
S1/2 38 1
S0 39 2
D3/2 40 3
F2 41 6
D1/2 42 7
S3 43 6
S5/2 44 5
F5 45 4
F9/2 46 1
S0 47 2
S1/2 48 1
S0 49 2
°
P1/2 50 3
P0 51 4
°
S3/2 52 3
P2 53 2
°
P3/2 54 1
S0

5
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
85.468 87.62 88.906 91.224 92.906 95.95 (97) 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29
2 2 2 2 4 5 5 2 7 8 10 10 10 2 10 2 10 2 2 10 2 3 10 2 4 10 2 5 10 2 6
[Kr]5s [Kr]5s [Kr]4d5s [Kr]4d 5s [Kr]4d 5s [Kr]4d 5s [Kr]4d 5s [Kr]4d 5s [Kr]4d 5s [Kr]4d [Kr]4d 5s [Kr]4d 5s [Kr]4d 5s 5p [Kr]4d 5s 5p [Kr]4d 5s 5p [Kr]4d 5s 5p [Kr]4d 5s 5p [Kr]4d 5s 5p
4.1771 5.6949 6.2173 6.6341 6.7589 7.0924 7.1194 7.3605 7.4589 8.3369 7.5762 8.9938 5.7864 7.3439 8.6084 9.0097 10.4513 12.1298
55 2
S1/2 56 1
S0 72 3
F2 73 4
F3/2 74 5
D0 75 6
S5/2 76 5
D4 77 4
F9/2 78 3
D3 79 2
S1/2 80 1
S0 81 2
°
P1/2 82 3
P0 83 4
°
S3/2 84 3
P2 85 2
°
P3/2 86 1
S0

6
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Cesium Barium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
132.91 137.33 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98 (209) (210) (222)
2 14 2 2 14 3 2 14 4 2 14 5 2 14 6 2 14 7 2 14 9 14 10 14 10 2 2 3 4 5 6
[Xe]6s [Xe]6s [Xe]4f 5d 6s [Xe]4f 5d 6s [Xe]4f 5d 6s [Xe]4f 5d 6s [Xe]4f 5d 6s [Xe]4f 5d 6s [Xe]4f 5d 6s [Xe]4f 5d 6s [Xe]4f 5d 6s [Hg]6p [Hg]6p [Hg]6p [Hg]6p [Hg]6p [Hg]6p
3.8939 5.2117 6.8251 7.5496 7.8640 7.8335 8.4382 8.9670 8.9588 9.2256 10.4375 6.1083 7.4167 7.2855 8.414 9.3175 10.7485
87 2
S1/2 88 1
S0 104 3
F2 105 4
F3/2 106 0 107 5/2 108 4 109 110 111 112 113 114 115 116 117 118

7
Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
Francium Radium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
(223) (226) (267) (268) (269) (270) (269) (278) (281) (282) (285) (286) (289) (289) (293) (294) (294)
2 14 2 2 14 3 2 14 4 2 14 5 2 14 6 2
[Rn]7s [Rn]7s [Rn]5f 6d 7s [Rn]5f 6d 7s [Rn]5f 6d 7s [Rn]5f 6d 7s [Rn]5f 6d 7s
4.0727 5.2784 6.02 6.8 7.8 7.7 7.6

Atomic Ground 57 2
D3/2 58 1
G°4 59 4
°
I9/2 60 5
I4 61 6
H°5/2 62 7
F0 63 8
S°7/2 64 9
D°2 65 6
H°15/2 66 5
I8 67 4
°
I15/2 68 3
H6 69 2
F°7/2 70 1
S0 71 2
D3/2
Lanthanides

Number State
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Symbol
58 1
G°4 Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
138.91 140.12 140.91 144.24 (145) 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97

Name
Ce [Xe]5d6s
5.5769
2
[Xe]4f5d6s
5.5386
2 3 2
[Xe]4f 6s
5.4702
4 2
[Xe]4f 6s
5.5250
5 2
[Xe]4f 6s
5.577
6 2
[Xe]4f 6s
5.6437
7 2
[Xe]4f 6s
5.6704
7
[Xe]4f 5d6s
6.1498
2 9 2
[Xe]4f 6s
5.8638
10 2
[Xe]4f 6s
5.9391
11 2
[Xe]4f 6s
6.0215
12 2
[Xe]4f 6s
6.1077
13 2
[Xe]4f 6s
6.1843
14 2
[Xe]4f 6s
6.2542
14
[Xe]4f 5d6s
5.4259
2

Cerium
Standard 140.12 89 2
D3/2 90 3
F2 91 4
K11/2 92 5
L°6 93 6
L11/2 94 7
F0 95 8
°
S7/2 96 9
D°2 97 6
H°15/2 98 5
I8 99 4
°
I15/2 100 3
H6 101 2
F°7/2 102 1
S0 103 2
°
P1/2
Actinides

Atomic
†
Weight (u)
[Xe]4f5d6s
2
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
5.5386 Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
(227) 232.04 231.04 238.03 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (266)
Ground-state Ionization [Rn]6d7s
2 2 2
[Rn]6d 7s
2
[Rn]5f 6d7s
2 3
[Rn]5f 6d7s
2 4
[Rn]5f 6d7s
2 6 2
[Rn]5f 7s
7 2
[Rn]5f 7s
7
[Rn]5f 6d7s
2 9 2
[Rn]5f 7s
10 2
[Rn]5f 7s
11 2
[Rn]5f 7s
12 2
[Rn]5f 7s
13 2
[Rn]5f 7s
14 2
[Rn]5f 7s
14 2
[Rn]5f 7s 7p
Configuration Energy (eV) 5.3802 6.3067 5.89 6.1941 6.2655 6.0258 5.9738 5.9914 6.1978 6.2817 6.3676 6.50 6.58 6.66 4.96

† 12
Based upon C. () indicates the mass number of the longest-lived isotope. For the most precise values and uncertainties visit [Link] and [Link]/data.
NIST SP 966 (July 2019)

Chapter One: Gases Formula Sheet Chapter Two: Thermodynamics & Thermochemistry Formula Sheet
Chemistry 105 Equation Sheet Chemistry 106 Equation Sheet °
Moles, Molar Mass, Mass Avogadros #, Moles, Molecules Density
Work
W = P ext ΔV
Internal Energy
ΔE = q + w
Heat
q = C ΔT
Heat
q = mcΔT
Constants ℎ Constants Pressure
∆ ∆ ≥  °1/2 # ! #
a0 = 0.5291772059 Å Pressure  c = 2.99792458 × 108 m/s 1 atm = 760 torr *  =    ! = $
% = %&
' = ( Enthalpy Molar Enthalpy Standard Enthalpy Change

c = 2.99792458 × 108 m/s 1 atm = 760 torr *    e = 1.6021765 x 10-19 C = 101325 Pa *   ΔH
= RS (  −  ) F = 9.648534 × 104 C mol-1 = 406.783 in H2O =  + ΔH = ΔE + P ΔV ΔH x = n
ΔH°rxn = ΣH°(prod.) ΣH°(reac.)
e = 1.6021765 x 10-19 C = 101325 Pa * H   [] [] Ideal Gas Law Ideal Gas Law & Molar Mass & Density
ɛ0 = 8.8541877 x 10-12 F/m = 406.783 in H2O h = 6.626 × 10-34 J·s = 14.6959 lb/in2 (psi) [] '*+ Simple Calorimetry Heat Exchange Heat Exchanged By Solvent w.r.t c
h = 6.626 × 10-34 J·s = 14.6959 lb/in2 (psi)
V(r) =
_1 _2
kB = 1.38065 × 10-23 J/K 1 torr = 1 mm Hg (at 0 °C)* t½ = )( = !*+ $ = )
4bc0 e  q surr = q sys q rxn = (q sol + q cal ) q sol = msol csol ΔT sol
kB = 1.38065 × 10-23 J/K 1 torr = 1 mm Hg (at 0 °C)*   KB (water) = 0.51 °C/m 1 Pa = 1 kg·m-1·s-2* t½ =
.693
f =  KF (water) = 1.86 °C/m 1 bar = 100,000 Pa * ã Boyle's Law Charles Law Combined Gas Law
,·.2 1 Pa = 1 kg·m-1·s-2*   Calorimeter Calibration: Option One Calorimeter Calibration: Option Two
ke = 8.987551 × 109 Kw = 1.0 × 10-14 Energy t½ = (1 (2 ) 1( 1 ) 2( 2
02 ã[ç]0
me = 9.109383 × 10-31 kg
1 bar = 100,000 Pa * μ = Qr
me = 9.109383 × 10-31 kg 1 J = 1 kg·m2/s2 = 0.2390cal 7 ) 1( 1 = ) 2( 2 +1
= +2 +1
= +2
q water = q cal q cal = C cal ΔT cal = q rxn
ln = − + ln  q
mn = 1.6749273 × 10-27 kg
Force
ΔE = q + w mn = 1.6749273 × 10-27 kg 1 J = 1 V·C = 0.009869 L·atm Rz mH2O cH2O ΔT H2O = (C cal ΔT cal ) C cal = ΔTrxn
mp = 1.6726217 × 10-27 kg mp = 1.6726217 × 10-27 kg 1 eV = 1.602 × 10-19 J  7   Dalton’s Law of Partial Pressure Mole Fraction Partial Pressure
cal
1 N = 1 kg·m·s-2 ∆Euniv = 0 ln   = −  −  mH2O cH2O ΔT H2O
NA = 6.022142 × 1023 mol-1 NA = 6.022142 × 1023 mol-1 1 Watt = 1 J/s  R z z !& C cal = ΔT cal
1
∆Suniv ≥  1 97 ßN9 − 97 )+ = )& + )/... 1& = )& = 1 & • )+
R = 8.31447 R = 8.31447  L∙atm = . J ln  = !+
.23∙5 Power S = kB ln W .23∙5 ßN9 Rz Bomb Calorimeter Heat Bomb Calorimeter Enthalpy
6 ∙ 7. 6 ∙ 7. 1 Ampere = 1 C/s
= 0.0820575 1 Watt = 1 J/s = 0.0820575 pX = ̶ log X q rxn = (q cal + q H2O ) = (C cal + cH2O mH2O )ΔT ΔH = ΔE + Δngases RT
.23∙5 q = mCΔT .23∙5 Radioactivity Average Molar Mass of Gas Mixture Avg. 34of Gas Molecule Avg. Molecule Speed
973 Conversions (* = exact) [é]
= 1.987207 1 Curie (Ci) = 3.7 × 1010 pH = pKa + log 1 2
w = ̶ Pext ΔV [ç] Hess’s Law For Reaction: aA + bB →cC + dD
.23∙5 Energy Length disintegrations/s = 1 Bq Q = mCΔT
$567. = 1&$& + 1/$/... Ē = 2
#ū
RH =1.0974 × 107 m-1 1 J = 1 kg·m2/s2 = 0.2390cal ΔH = ΔE + PΔV 1 in = 2.54 cm* ΔH°rxn = [cΔH°f (C) + dΔH°f (D)] [aΔH°f (A) + bΔH°f (B)]
1 Gy = 1 J/kg ΔE = q + w 2
ey 1 ft = 12 inches* 3*+
1 J = 1 V·C = 0.009869 L·atm
∆w = Formulas °
∆eÇN °
= ΣÑ,Üe2á ū = $ Total Bond Enthalpy
Conversions (* = exact) 1 eV = 1.602 × 10-19 J z 1 yd = 3 ft* ρ = m/V
Length 1 L∙atm = 101.3 J ΔG = ΔH – TΔS 1 m = 39.37 inches* 9℉
°
− ΣÑ,e79 Root Mean-Square Speed of Gas Molecule Root Mean-Square Speed of 2 Diff. Gas Molecules
T BE = ΔH°rxn = ΣH°(prod.) ΣH°(reac.)
TF = ·TC + 32 °F
1 in = 2.54 cm* ΔG = ΔG° + RT ln Q 1mile = 5280feet* = 1.609km 5℃
5 °
∆eÇN ≈ Σâäe2ãN Enthalpy Change of Gas Phase Reactions
1 ft = 12 inches* ° ° ° Mass TK = ·TC + 273.15 K 3*+ ;<#=(&) $/
Formulas ∆eÇN = ΣÑ,Üe2á − ΣÑ,e79 ℃
;<#= = = **heavier M in numerator** ΔH°rxn = ΣT BE(reac.) ΣT BE(prod.)
1 yd = 3 ft* 1 lb = 453.59237 g Ptot = P1 + P2 + P3 + . . . − ΣâÑ2e.á $ ;<#=(/) $&
ρ = m/V
1 m = 39.37 inches*
°
∆eÇN ≈ Σâäe2ãN = 16 oz. avdp.* ú ∆y7Ü   ΔG = ΔH – TΔS
ΔH°rxn = Σenthalpies of bonds broken enthalpies of bonds f ormed
TF =
9℉
TC + 32 °F ln   =  −  Graham’s Law
1mile = 5280 feet* 5℃ − ΣâÑ2e.á 1 US lb = 12 troy ounces * ú R z z ΔGrxn° = ̶ RT·ln K Boltzmann Equation (W=# of microstates) Entropy Contributions
1mile = 1.609 km 1 ton = 2000 lb * PV = nRT  ΔH°  
TK =
5
TC + 273.15 K PV = nRT ln  =−  −  <@EE(&) $/ S=k ln(W ) ΔS univ = ΔS sys + ΔS surr > 0
Mass ℃
Ptot = P1 + P2 + P3 + . . .
1 amu = 1.660538 × 10-24 g Psolv = X solv P°solv  R z z @!<ABℎ#@!D E5BDF< (E) = <@EE(/)
= $&
1 lb = 453.59237 g c = λν Volume Cg = kHPg ΔG = ΔG° + RT·ln Q Standard Molar Entropies
= 16 oz. avdp.* E = hν Rç zé êé 1 L = 1.05669 US qt.
ΔTb = i·KB·m
ΔG = ̶ nFE
Constants & Conversions
ΔS°rxn = ΣnS°f (prod.) ΣnS°f (reac.)
1 US lb = 12 troy ounces * = =√ 1 US gal = 4 US qt * w = ̶ Pext ΔV
Ré zç êç ΔTf = i·KF·m
ℎ = 128 US fl. ozs. * ey Entropy & Heat Flow Entropy & Heat Flow of System Only
1 ton = 2000 lb * H= Π = iMRT ∆w = * = 8. 314 I/4 • #FK(for Kpa) * = 0. 082507 O • 5D#/4 • #FK(for atm) * = 0. 08314 O • P5</4 • #FK(for
  1 US fluid oz. = 29.5735 mL z ΔH surr ΔH sys ΔH sys
1 amu = 1.660538 × 10-24 g 7y = Rz 933 = eá  − eá  bars) ΔS surr = T or = T ΔS sys = T >0
Ekinetic = ½ m2  1 cm3 = 0.001 L * S = kB·ln W
c = λν Rz 1 bar = 100Kpa = 0.9869atm = 750torr = 750mmHg = 14.5psi Entropy of Dissolution Entropy & Gases
1 in3 = 16.4 cm3 2
933 = 933 − ln 
Volume E = mc2 Rz f
e.ï =   = √ Time E = hν S solution > (S solvent + S solute ) ΔS = S A+B mixed (S A(g) + S B(g) ) > 0
1 US gal = 3.7854 L = 4 US qt * ê − ±   − 
Φ = ℎL - KEelectron 1 year = 3.15569 × 107 s E = mc2 =
1 US qt = 32 US fl. ozs. *  Gibbs Free Energy Gibbs Equation
RS ℎ pX = ̶ log X Force A = kN
1 US fluid oz. = 29.5735 mL [S  ]¨≠
N = −P  1 N = 1 kg·m·s-2 [A]t = -kt + [A]0 % ionization = × % ΔG = ΣG(prod.) ΣG(reac.) ΔG = ΔH T ΔS
1 cm3 = 0.001 L *  Kw = [H3O+][OH-] SçÆ
ln [A]t = – kt + ln [A]0 N±°
1 in3 = 16.4 cm3 log K =
.59

* = exact ν = frequency  = * * = exact ν = frequency  = *

© Updated 9/18/2018 BYU Department of Chemistry and Biochemistry © Updated 9/18/2018 BYU Department of Chemistry and Biochemistry

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