Dr.

Mohamed Fadel

1
 A Green Chemistry Module

Petretec – Dupont’s Technology for Polyester

Regeneration

Presidential Green Chemistry Challenge Award

2
World Proven Reserves of Crude Oil

20.6 65.4
63.7 44.0
675.7
74.9
89.5

thousand million barrels

3
World Proven Crude Oil Reserves
South & Central
North America
America
6%
9%
Europe
2%
Africa
7%
Middle East Former Soviet Union
66% 6%
Asia & Pacific
4%
as percent of 1296 thousand million barrel total

4
 Composition of Crude Oil
CRUDE OIL

HYDROCARBONS NON-HYDROCARBONS

ALIPHATICS AROMATICS NAPHTHENES SULFURS NITROGENS OXYGENS METALLICS

25% 17% 50% <8% <1% <3% <100PPM

C1 - C60 (C6H5)n O
CYCLOALKANES
SH

N
H COOH
S

5
 Crude Oil Classification

PETROLEUM
Saturates Asphaltics
n-alkanes C5 - C44 nitrogen
branched alkanes
Aromatics oxygen containing compounds
cycloalkanes (napthenes) single ring sulfur
condensed ring

Ot h e r
10% S a t ur a t e s
A sp h a l t i c s
25%
8%

A r oma t i c s
7%

API Gravity = 35o

N a pht he ne s
50%

6
 The Uses of Crude Oil
Uses of Crude Oil

Uses of Crude Oil

Gasoline Distillate Fuel Oil

Kerosene Jet Fuel Residual Fuel Oil
Gasoline Liquefied Refinery Gases Distillate
Still Gas Fuel Oil
Kerosene JetCoke
Fuel Residual Fuel Oil
Asphalt and Road Oil
Liquefied Refinery
PETROCHEMGasesICAL FEEDSTOCKS Still
LubricantsGas
Kerosene Other
Coke Asphalt and Road Oil
PETROCHEMICAL FEEDSTOCKS Lubricants
Kerosene Other

7
 The Xylenes
CH3 CH3 CH3
CH3

CH3
CH3
ortho meta para
o o o
Boiling Point 144 C 139.3 C 137-138 C
o o o
Melting Point -25 C -47.4 C 13-14 C
8
Crude oil is separated into
fractions by fractional
distillation. The fractions at
the top of the fractionating
column have lower boiling
points than the fractions at
the bottom. The heavy
bottom fractions are often
cracked into lighter, more
useful products. All of the
fractions are processed
further in other refining units

9
CRUDE Petroleum delivered from well
field
DESALTING
Water washing to remove
impurities
REFINING Distillation to separate by boiling
point ranges
REFORMING
Conversion reactions to alter
molecular structures
BLENDING Mixing to obtain maximum
commercial characteristics 10
 Petroleum Refining
C1-C4
GAS bp < 50 oF

C5 - C?
T LIGHT NAPHTHA
bp 50-200oF

O HEAVY NAPHTHA
C? - C12
bp 200-400oF
W
C12 - C16
E KEROSENE
bp 400-500oF
CRUDE DESALTER FURNACE
R ATM. GAS OIL C15 - C18
bp 500-650oC

> C20
RESIDUUM
bp >650oF

Distillation – separation by boiling point

11
Chemical and physical properties

12
 Matter
• Every element/compound is unique in
some way from all others.
• If you know enough about a substance,
you can figure out what it is.
• If you know what a substance is, you
can know all types of things about it.

13
 Matter

All matter has 2 types of properties:

 Physical properties and
 chemical properties.

14
 Physical properties

• A physical property is a characteristic

of a substance that can be observed
without changing the substance into
another substance.
– (You can see it without changing what
you’re looking at into something else.)

15
 Physical Properties
• Physical properties can be extensive or
intensive:
– Extensive properties depend on the amount of
a substance that you have.
– Intensive properties don’t depend on how
much you have.

16
 Physical Properties - Examples

• Examples of extensive
physical properties
include:
– Volume
– Mass
– Weight
– Size

17
 Physical Properties - Examples
• Examples of intensive physical
properties include:
– Density
– Melting point
– Boiling point

18
 Physical Properties - Examples
• Other physical properties include:
– Color
– Hardness
– Odor
– Taste
– State of matter
– Texture
– Luster (shine)
– Flexibility
– Heat conductivity
– Electrical conductivity
– Solubility (ability to dissolve in water.)
– Shape
– Viscosity
– Ductility
– Malleability 19
 Chemical properties
• A Chemical property is a
characteristic of a substance
that can only be observed by
changing it into a different
substance.

20
 Chemical properties - Examples
• Examples of chemical properties
include:
– The ability to burn
– Ability to tarnish
– Ability to rust
– Ability to decompose
– Ability to react with other
chemicals
– Instability
– Ability to do acid/base
reactions
21
 Chemical and physical properties – So what?
• Titanium is very strong and
doesn’t rust, so it is often used
in jet engines.
• Titanium is also
nonallergenic. This,
combined with the fact that it
is rust proof makes it great for
artificial joints as well as
piercings.
22
 Chemical and physical properties – So what?
• Tungsten is usually used
as the filament in
lightbulbs because it has
the highest melting point of
any metal.
• It glows red hot when
electricity runs through it,
and it gives off both heat
and light. 23
 Chemical and physical properties – So what?
• Sulfur smells awful. Rotten
eggs, onions, and garlic all
have sulfur in them. Stink
bombs use sulfur to create
a bad smell.
• Sulfur is also flammable,
and it is one of the 3 main
ingredients in gun powder.
24
 Chemical and physical properties – So what?
• Chromium is famous
for its intense luster.
Chrome plated tools,
jewelry, silverware, or
car parts are very
popular.

25
 Element abundance
• The most common element
in the universe is Hydrogen
(about 75%), and Helium
(about 25%).
• The most common element
on Earth is Oxygen (46.6%),
and Silicon (27.7%).
• The most common element
in your body is Oxygen
(65%), and Carbon (18%) 26
Chemical and physical changes

27
 Physical Change
• A Physical change is a change
in a substance that does not
change what the substance is.

28
 Physical Change - examples
• Examples of physical
change include:
– Change in shape
– Change in size
– Change in phase
• Melting (solid to liquid)
• Boiling (liquid to gas)
• Evaporation (liquid to gas)
• Condensation (gas to liquid)
• Freezing (liquid to solid)
• Sublimation (solid to gas)
• Deposition (gas to solid)

29
 Physical Change
• Physical changes might be caused by:
– Grinding
– Cutting
– Crushing
– Bending
– Breaking
– Heating/cooling
• (change in phase)
– squishing

30
 Physical Change
• Evidence that a physical change
has occurred might include:
– Change in shape
– Change in form
– Change in size
– Change in phase (This is always
a physical change!)
– Physical changes are usually
reversible

31
 Chemical change
• Chemical changes occur
when a chemical reaction
causes bonds between
atoms to break or to form.

32
Chemical change – Chemical reactions
• There are 5 types of chemical reactions
that cause chemical changes to occur.
1- Composition reactions
– Two things come together to form
something new
– A + B = AB
– 2H2 + O2  2H2O
2- Decomposition reactions
– 1 thing breaks apart to form 2 or
more things.
– AB = A + B
– 2H2O  2H2 + O2

33
Chemical change – Chemical reactions
3- Single replacement reactions
– One atom replaces another atom
– A + BC = AC + B
or
A + BC = AB + C
– Mg + 2HCl  H2 + MgCl2
4- Double replacement reactions
– Two chemicals switch places
– AX + BY = AY + BX
– 2KI + Pb(NO3)2  PbI2 + 2KNO3
5- Combustion reaction
– A substance combines with oxygen and releases energy.
34
– C3H8 (propane) + 5O2  3CO2 + 4H2O
 Chemical Change: Evidence
• Evidence that a chemical change
has occurred might include:
– A color change
– An odor change
– Formation of a precipitate (you mix
two liquids and make a solid)
– Gas is formed (bubbles)
– Changes in physical properties.

35
 Physical and Chemical change
• During a chemical change
energy can be released in
the form of:
– Heat
– Light

36
Chemical change – Chemical reactions
• When a chemical
change occurs,
energy is either
released or absorbed.

37
 Physical and Chemical change - heat
• A chemical reaction that
releases energy in the form
of heat is called
exothermic.
– Heat comes OUT
• Exo = out
• Thermic = heat
– It will feel HOT.

38
 Physical and Chemical change - heat
• A chemical reaction that
absorbs energy in the
form of heat is called
endothermic.
– Heat goes IN
• Endo = in
• Thermic = heat
– It will feel COLD
39
Gas and Gas Law

40
 CONTENTS

1. Units of Measurement
2. Substances That Exist as Gases
3. Pressure of a Gas
4. The Gas Laws
5. The Ideal Gas Equation
6. Gas Stoichiometry
7. Dalton’s Law of Partial Pressures
8. The Kinetic Molecular Theory of Gases
9. Deviation from Ideal Behavior

41
 Units of
Measurement
42
Every measurement must have a unit.

43
 SI Units

 Système International d’Unités

 Uses a different base unit for each quantity

44
Metric System

45
 Metric System
Prefixes convert the base units into units that are
appropriate for the item being measured.

46
Units of Measurement: Length

47
 Volume

 The most commonly used metric

units for volume are the liter (L) and
the milliliter (mL).
□ A liter is a cube 1 dm long on each side.
□ A milliliter is a cube 1 cm long on each side.

48
Volume

49
Units of Measurement: Volume

50
Units of Measurement: Mass

51
Units of Measurement: Temperature

K = C + 273.15
F = 9/5(C) + 32
C = 5/9(F − 32)
52
 Density

Physical property of a substance

mass
Density 
Volume
m
d 
V

53 53
DENSITY

54 54
Gases

55
 STATES OF MATTER

SOLID LIQUID GAS PLASMA

Tightly packed, in a Close together with no Well separated with Has no definite volume
regular pattern Vibrate, regular arrangement. no regular or shape and is
composed of electrical
but do not move from Vibrate, move about, and arrangement.
charged particles
place to place slide past each other Vibrate and move
freely at high speeds

56
Under certain conditions of pressure and temperature, most
substances can exist in any one of three states of matter: solid,
liquid, or gas.
For example: water (H2O) can be solid ice, liquid water, Steam
or water vapour (Gas)

57
Difference between Gas and Vapour:
Gas Vapour
Is gas at normal temperature (250C ) and Is a liquid or a solid at normal temperature
pressure (1 atm) and pressure
At 250C and 1 atm O2 is a gas At 250C and 1 atm H2O is a vapour

Properties of Gas

1- Molecular motion in gases is random

2- Attraction forces between gas molecules are so small so that each
molecule moves freely and essentially independently of other
molecules.

3- The study of gas behavior as a function of temperature and pressure

play an important role in the development of the atomic theory of matter
and the kinetic molecular theory of gases.
58
Substances that exist as gases under normal atmospheric
conditions, which are defined as 25°C and 1 atmosphere (atm)
pressure:
1. Elements that exist as gases at 25oC and 1 atm. The noble
gases (the Group 8A elements) are monatomic species; other
elements exist as diatomic molecules. Ozone (O3) is also a gas.

59
2. Ionic compounds do not exist as gases at 25°C and 1
atm, because cations (+) and anions (-) in an ionic solid are
held together by very strong electrostatic forces. To overcome
these attractions we must heat the solid. For example, NaCl
melts at 801°C. In order to boil it, we would have to raise the
temperature to well above 1000°C.
3. Molecular compounds boil at lower temperatures than ionic
compounds. (Example: CO, CO2, HCl, NH3, and CH4). The
stronger intermolecular forces, the less possible a
compound can exist as a gas at normal temperatures.
O2 is essential for our survival. Hydrogen sulfide (H2S) and
hydrogen cyanide (HCN) are deadly poisons. CO, NO2, O3,
and SO2, are less toxic.
60
The gases He, Ne, and Ar are chemically inert. Most gases are
colorless. Exceptions are F2, Cl2, and NO2. The dark-brown
color of NO2 is sometimes visible in polluted air.

61
Physical characteristics of gases:
1. Gases assume the volume and shape of their containers.

2. Gases are the most compressible of the states of matter.

3. Gases mix evenly and completely when kept in the same container.
4. Gases have much lower densities than liquids and solids.
62
Pressure of Gas:
Gases exert pressure on any surface with which they come
in contact, because gas molecules are in motion.
Force Force
Units of Pressure: Pressure   2
(1)
Area m
𝐹𝑜𝑟𝑐𝑒=𝑚𝑎𝑠𝑠 𝑋 𝑎𝑐𝑐𝑒𝑙𝑒𝑟𝑎𝑡𝑖𝑜𝑛=𝑘𝑔 𝑋 𝑎𝑐𝑐𝑒𝑙𝑒𝑟𝑎𝑡𝑖𝑜𝑛 (2)
From the second law of motion (Newton):
velocity velocity
accelerati on   (3)
time s
distance m
velocity   (4)
time s
m velocity
accelerati on   (5)
ss s2

63
The SI unit of force is the newton (N):
m
From (2) Force  kg  2  1 N (6)
s
1 N is roughly equivalent to the force exerted by Earth’s gravity
on an apple.

International System (SI) Unit of Pressure:

The SI unit of pressure is the Pascal (Pa): defined as
one newton per square meter:
N
Pressur  1 2
 1 Pa
m

64
Atmospheric Pressure:
 The density of air decreases with increasing distance from
Earth.

 The denser air exerts the greater pressure.

 Atmospheric pressure is the pressure exerted by Earth’s
atmosphere. 65
The actual value of atmospheric pressure depends on:

➊ Location ➋ Temperature ➌ Weather conditions

 At the molecular level, air pressure results from

collisions between the air molecules and any surface
with which they come in contact.

66
How is atmospheric pressure measured?
The atmospheric pressure measured by the BAROMETER
instrument.

67
Standard atmospheric pressure (1 atm) = the pressure that
supports a column of mercury exactly 760 mm (or 76 cm)
high at 0°C at sea level.
1 torr = 1 mmHg
1 atm = 760 mmHg=760 torr
1 atm = 1.01325 x 105 Pa
1 atm = 1.01325 x 102 kPa = 101.325 kPa

68
Example
The pressure outside a plane flying at height falls below standard
atmospheric pressure. Therefore, the air inside the cabin must be
increased to protect the passengers. What is the pressure in
atmospheres in the cabin if the barometer reading is 688 mmHg?

Solution:
1 atm = 760 mmHg

x atm = 688 mmHg

x atm X 760 mmgH = 688 mmHg X 1 atm

688 mmHg  1 atm

X atm   0.905 atm
760 mmHg
69
Practice Exercise Convert 749 mmHg to atmospheres.
Example:
The atmospheric pressure in Benghazi on a certain day
was 732 mmHg. What was the pressure in kPa?
Solution:
1 atm = 1.01325 X 102 kPa and 1 atm = 760 mmHg
1.01325 X 102 kPa = 760 mmHg

x kPa = 732 mmHg

7 3 2 m m Hg 1 0 1 . 2 3 5K P a
X kp a   9 7 . 6K P a
7 6 0 m m Hg

70
Practice Exercise Convert 295 mmHg to kilopascals.
How is gas pressure measured?
Manometer is used to measure the pressure of gases
other than the atmosphere.
There are two types of manometers:
1. The closed-tube manometer is used to measure
pressures below atmospheric pressure.
2. The open-tube manometer is used to measure
pressures equal to or greater than atmospheric pressure.

71
Closed-tube Open-tube

72
73
WHY? barometers and manometers use mercury (Hg)
as the working fluid, despite the fact that it is a toxic
substance.
Because Hg has a very high density (13.6 g/mL)
compared with most other liquids. And height of the
liquid in a column ( h)  1
. liquid density
This property enables the construction of small
barometers and manometers

74
Gas Laws:

75
 Boyle’s Law
Robert Boyle (1627-1691). Son of Earl of Cork, Ireland.

1. Boyle’s law: (P & V) (at constant n & T)

76
As P (h) increases V decreases
1
Pα
V
1
P  K1 
V
PV  K 1
77
When the temperature and amount of gas are constants: the
P x V is always equal to the same constant. Therefore:
𝐏𝟏𝐕𝟏 = 𝐤𝟏 & 𝐏𝟐𝐕𝟐 = 𝐤𝟏
𝐏𝟏𝐕𝟏 = 𝐏𝟐𝐕𝟐

78
Example
An inflated balloon has a volume of 0.55 L at sea level (1.0 atm) and is
allowed to rise to a height of 6.5 km, where the pressure is about 0.40
atm. Assuming that the temperature remains constant, what is the final
volume of the balloon?
Solution: Note that the number of moles and temperature of the gas are
kept constant; therefore, we need Boyle’s law
Where P1V1 = P2V2

Initial conditions Final conditions

P1 = 1.0 atm p2 = 0.40 atm
V1 = 0.55 L V2 =?

Comment: When pressure is reduced (at constant temperature), volume increases. The final volume is
greater than the initial volume, so the answer is reasonable.
79
 Charles’s Law
Jacques Charles (1746-1823). Isolated boron and studied gases. Balloonist

• 2. Charles’s and Gay-Lussac’s Law: (V & T) (at constant n & P)

• At constant amount of gas and pressure, the volume is directly proportional to the
temperature of the gas.
Vα T
V  K2  T
V
 K2
T

80
81
Variation of gas volume with temperature at constant
pressure:

When the pressure and amount of gas are constants: the VT

is always equal to the same constant. Therefore:
V1 V2
 K2 &  K2
T1 T2
V1 V
 2
T1 T2

82
Temperature (T) must be in Kelvin (K) T (K) = T (oC) + 273.15
Absolute zero:
theoretically it's the lowest attainable temperature (-273.15 oC).
Kelvin Scale Celsius Scale
Absolute zero 0K -273.15 oC
Freezing point of water 273.15 K 0 oC
Boiling point of water 373.15 K 100 oC

83
Example
A 452 mL sample of fluorine gas is heated from 22 0C to 187 0C at
constant pressure. What is its final volume?
Solution:
This change occurs at constant pressure and number of moles of the
gas, so we can apply Charles’s law.
Where

Initial conditions Final conditions

V1 = 452 mL V2 =?
T1 = (22 + 273) K = 295 K T2 = (187 + 273) K = 460K

Comment As you can see, when the gas is heated at constant pressure, it
expands. 84
3. Another form of Charles’s and Gay-Lussac Law: (P & T) (at
constant n & V)
At constant amount of gas and volume, the pressure is directly
proportional to the temperature of the gas.
Joseph Louis Gay-Lussac (1778-1850)

Pα T
P P1 P2
P  K3  T &  K3  
T T1 T2
85
Example
A sealed storage tank contains argon gas at 18 0C and a pressure of
875 kPa at night. What is the new pressure if the tank and its contents
warm to 32 0C during the day ?
Solution
This change occurs at constant volume and number of moles of the
gas, so we can apply Gay law.
Where

Initial conditions Final conditions

P1 = 875 kPa P2 = ?
T1 = (18 + 273) K = 291 K T2 = (32 + 273) K = 305 K

86
4. Avogadro’s Law: (V & n) (at constant P & T)
At constant pressure and temperature, the volume
of a gas is directly proportional to the number of
moles of the gas.
Vα n
V V1 V2
V  K4  n &  K4  
n n1 n 2
As the number of gas particles are increased, the volume of
the balloon also increases.

87
Example:
3H2 (g) + N2 (g) → 2NH3(g)

88
Since, at the same temperature and pressure, the volumes of the gases are
directly proportional to the number of the gases present, we can write
3H2 (g) + N2 (g)  2NH3 (g)
3 volumes + 1 volume  2 volumes
The volume ratio of molecular hydrogen to molecular nitrogen is 3:1, and that
of ammonia (the product) to molecular hydrogen molecular nitrogen (the
reactants) is 2:4, or 1:2 (figure 5.9).

Example : Ammonia burns in oxygen to form nitric oxide (NO) and

water vapor. How many volumes of NO are obtained from one volume
of ammonia at the same temperature and pressure?

4NH3 + 5O2 4NO + 6H2O

1 mole NH3 1 mole NO
At constant T and P
1 volume NH3 1 volume NO

89
 The ideal gas equation
( describes the relationship among the four variables P, V, T, and n)
An ideal gas is a hypothetical gas whose pressure-volume-temperature
behavior can be completely described by the ideal gas equation.

90
Gas constant (R):
Experiments show that under these conditions:
 1 mole of an ideal gas occupies 22.414 L.
 The condition 0 oC and 1 atm are called standard
temperature and pressure (STP).

91
 Values of R in Different Units
Atm x L
R* = 0.082
Mol x K
R = 62.36 Torr x L
Mol x K
R = 8.314 kPa x dm3
Mol x K
R = 8.314 J#
Mol x K
* Most calculations in this text use values of R to 3 significant figures.

#J is the abbreviation for joule, the SI unit of energy. The joule is a

derived unit composed of the base units kg x m2/s2

92
Example
Sulfur hexafluoride (SF6) is colorless, odorless, very uncreative gas. Calculate
the pressure (in atm) exerted by 1.82 moles of the gas in steel vessel of volume
5.43 L at 69.5 0C.
Solution This problem provides information about the number of moles,
volume, and temperature of a gas, but no change in any of the quantities occurs.
Therefore, to calculate the pressure we can use the ideal gas equation, which can
be rearranged to give.
Where

conditions
n = 1.82 moles P = ? (atm) R= 0.0821 L. atm/k.mol
V = 5.43 L T = (69.5 + 273) K

93
Example : Calculating the Value of R with P in kPa and V in
At pressure of 100 kPa and 298.15 K, 1.00 mole of gas occupies 24.789
L. What is the R value?
Solution Insert the value into the Ideal gas equation.
Where
Initial conditions Final conditions
P = 100 kPa n = 1.00 mole
V = 24.789 L R=?

P V 100kPa  24.789 L
R   8.314 L kPa mol-1 K-
n  T 1.00mol  298.15K 1

94
The modified form of the ideal gas equation:
The ideal gas equation is useful for problems that do not
involve changes in P,V, T, and n . If we know any three of
the variables we can calculate the fourth one using the
equation (PV= nRT). When conditions change, we must
employ a modified form of the ideal gas equation that takes
into account the initial and final conditions:
P2V2
(Before change) R  PV and
1 1
R
n2T2
(After change)
n1T1

P1V1 PV
R  R 2 2
n1T1 n2T2

95
Example:
An inflated helium balloon with a volume of 0.55 L at sea
level (1.0 atm) is allowed to rise to a height of 6.5 km, where
the pressure is about 0.40 atm. Assuming that the temperature
remains constant, what is the final volume of the balloon?
Solution: P1V1 P2V2

n1T1 n2T2
Because n1 = n2 and T1 = T2 (Constants): P1V1 = P2V2
(Before change) (After change)
V1 = 0.55 L P1=1.0 atm P2= 0.40 atm V2=?
P1V1
V2 
P2
1.0 atm  0.55 L
V2   1.4 L
0.40 atm
96
PRACTICE EXERCISE
A gas initially at 4.0 L, 1.2 atm, and 66 oC undergoes a change
so that its final volume and temperature become 1.7 L and 42
oC. What is its final pressure? Assume the number of moles

remains unchanged.
Example: Argon is an inert gas used in light bulbs to retard the
vaporization of the filament. A certain light bulb containing
argon at 1.20 atm and 18 0C is heated to 85 0C at constant
volume. What is the final pressure of argon in the light bulb
(in atm)?
Solution: The volume and amount of the gas are unchanged,
so V1 = V2 and n1 = n2 . Equation (3.7) can therefore be written
Where

97
Initial conditions Final conditions
P1=1.20 atm P 2= ?
T1 = (18 + 273.15) = 291.15 K T2= (85 + 273.15) = 358.15 K

98
Density Calculations:
PV= nRT (Ideal gas equation)
By rearrange the ideal gas equation, we can calculate the
density of a gas: V RT
n

P

The number of moles of the gas, n = 𝑚ℳ

Where 𝑚 is the gas mass (g) and ℳ is its molar mass (g/mol),
n P
therefore: 
MV RT
m
Because density, d
V
we can write:
d P PM
 or d 
M RT RT
 Gas density unit is in (g/L) rather than (g/mL)
 Density is intensive property, independent of the
amount of substance.
99
Example:
Calculate the density of carbon dioxide (CO2) in (g/L) at
0.99 atm and 55 oC. (C = 12.01, O = 16)
Solution:
T = (55+ 273)K = 328 K and ℳ = (12.01+16x2) = 44.01 g/mol
g
0.99 atm  44.01
PM mol  1.62 g/L
d 
RT 0.0821 L.atm  328 K
K.mol

Practice Exercise:
What is the density (in g/L) of uranium hexafluoride (UF6) at
779 mmHg and 62 oC?

100
The Molar Mass of a Gaseous Substance:
An apparatus for measuring the density of a gas. A
bulb of known volume is filled with the gas at a
certain temperature and pressure. First the bulb is
weighed, and then it is emptied and weighed again.
The difference in masses gives the mass of the gas.
Knowing the volume of the bulb, we can calculate
the density of the gas. Under atmospheric
conditions, 100 mL of air weigh about 0.12 g..

PM dRT
d by rearrangin g M 
RT P

101
Example:
A chemist has synthesized a greenish-yellow gaseous compound of
chlorine and oxygen and finds that its density is 7.71 g/L at 36 oC and 2.88
atm. Calculate the molar mass of the compound and determine its
molecular formula.( Cl = 35.45, O = 16)
Solution:
P = 2.88 atm, d= 7.71 g/L, T= (36+273)K =309 K

dRT 7.71 g/L  0.0821 L.atm.K-1 mol-1  309 K

M   67.9 g/mol
P 2.88 atm

102
Example:
Calculate the density of ammonia (NH3) in grams per liter (g/L) at
752 mmHg and 55oC.
Solution: To convert the pressure to atmospheres, we write

Using Equation (5.8) and T = 273 + 55 = 328 K, we have

103
GAS STOICHIOMETRY

104
Gas Stoichiometry:
 Stoichiometry is the study relationships between amounts
(in moles) and masses (in grams) of reactants and products
in chemical reactions. Mole ratio

Mole ratio Mole ratio Mole ratio

Mole ratio

Reactants Products
105
 When the reactants and/or products are gases, the
relationships between amounts (moles, n ) and volume (V)
can be used to solve problems.
 The key to solving stoichiometry problems is mole ratio,
regardless of the physical state of the reactants and
products.
 Gas laws also can be used in stoichiometry problems.

106
Example:
Calculate the volume of O2 (in liters) required for the complete combustion of 7.64 L of
acetylene (C2H2) measured at the same temperature and pressure.
2 C2H2 (g) + 5 O2 (g) → 4 CO2 (g) + 2 H2O (l)
Solution: T and P are constant → Avogadro's law
2 mol (C2H2) → 5 mol (O2) ……..…..… Stoichiometry
2 L (C2H2) → 5 L (O2)…………….…. Avogadro's law

7.64 L(C2H2) → x L (O2)

7.64 L (C2 H 2 )  5 L (O2 )
X L O2   19.1 L (O2 )
2 L (C2 H 2 )

Practice Exercise: Assuming no change in temperature and pressure,

calculate the volume of O2(in liters) required for the complete
combustion of 14.9 L of butane (C4H10):
2 C4H10(g) + 13 O2(g) → 8 CO2(g) + 10 H2O(l)

107
Dalton’s Law of Partial
Pressures

108
 O2 ;CO; CO2 ;NO2 ;NH3
CH4 ;NO
Air pollution
Study the pressure-volume-temperature relationship of a
sample of air, which contains several gases (mixtures of
gases):
Pair = PO2 + PCO + PCO2 + PNO2 +…………etc.
Pair = Total pressure and PO2 Partial pressure
The total gas pressure is related to partial pressures: (PT α
PP)
 The partial pressures: is the pressures of single gas
components in the mixture.
109
 Dalton's law (Dalton's law of partial pressures): in a
mixture of non-reacting gases, the total pressure exerted is
equal to the sum of the partial pressures of the single gases.
Consider a case in which two gases, 1 and 2, are in a
container of volume V:

P1 P2 PT = P1+ P2
110
The pressure exerted by gas A and gas B, according to the
ideal gas equation (PV= nRT), is:
n1RT n 2 RT
P1  and P2 
V V
Where n1 and n2 are the number of moles of gas 1 and gas 2
 In a mixture of gases 1 and 2, the total pressure PT is the result of
the collisions of both types of molecules, 1 and 2, with the walls of the
container. Thus, according to Dalton’s law:
PT = P1+ P2
n1RT n 2 RT RT
PT    PT  (n 1  n 2 )
V V V
n T RT
PT 
V
111
Where nT is the total number of moles of gases A and B (nT= n1+ n2)
In general, the total pressure of a mixture of gases is given by:
PT = P1+ P2+ P3+ …………..etc.
Where P1, P2 and P3 . . . are the partial pressures of components 1, 2, 3
How each partial pressure is related to the total pressure?
Dividing P1 by PT, we obtain:

RT
n1
P1 V

P RT
T (n 1  n )
2 V
n2
X1 
n1  n 2
112
Where X1 is called the mole fraction of gas 1.
 The mole fraction (Xi): is a unitless quantity represented
by the ratio of the number of moles of one gas to the total
number of moles of gases. Is given by:
P1
 X
P1 = X1 PT P 1
P2 = X2 PT T
P i = Xi P T
 The mole fraction is always smaller than 1. And the
sum of the mole fractions for a mixture of gases equal 1:
n1 n2 n1  n2
X1  X 2    1
( n1  n2 ) ( n1  n2 ) ( n1  n2 )

X1+ X2+ X3+………ect. = 1

113
How are partial pressures determined?
A manometer measures only the total pressure of a gaseous mixture. The
mole fractions, of the gases present are measured by mass spectrometer.
From mole fractions and total pressure, we can calculate the partial
pressures of individual components,
Example:
A mixture of gases contains 4.46 moles of neon (Ne), 0.74 mole of argon
(Ar), and 2.15 moles of xenon (Xe). Calculate the partial pressures of the
gases if the total pressure is 2.00 atm at a certain temperature.
Solution:

114
 n Ne 4.46 mol
X Ne  
n Ne  n Ar  n Xe 4.46 mol  0.74 mol  2.15 mol

4.46 mol
  0.607
7.35 mol
PNe = XNe PT = 0.607 X 2.00 atm = 1.21 atm
Simillarly
n Ar 0.74 mol
X Ar    0.1
n Ne  n Ar  n Xe 7.35 mol

PAr = XAr PT = 0.1 X 2.00 atm = 0.2 atm

115
 n Xe 2.15 mol
X Xe    0.293
n Ne  n Ar  n Xe 7.35 mol
PXe = XXe PT = 0.293 X 2.00 atm = 0.586 atm
Check: Make sure that the sum of the partial pressures is equal to the
given total pressure; that is, (1.21 + 0.2 + 0.586) atm = 2.00 atm.
Practice Exercise: A sample of natural gas contains 8.24 moles of
methane (CH4)), 0.421 mole of ethane (C2H6), and 0.116 mole of
propane (C3H8). If the total pressure of the gases is 1.37 atm, what are
the partial pressures of the gases?

Pi = Xi PT PT = 1.37 atm
0.116
Xpropane = = 0.0132
8.24 + 0.421 + 0.116
Ppropane = 0.0132 x 1.37 atm
116
Dalton’s law of partial pressures is for calculating volumes of gases
collected over water:
For example, when potassium chlorate (KClO3) is heated, it
decomposes to KCl and O2:
2 KClO3 (s) → 2 KCl(s) + 3 O2 (g)
The oxygen gas can be collected over water, as shown in Figure:

Figure: An apparatus for collecting gas over water. The oxygen generated by heating KClO3 in
the presence of a small amount of manganese dioxide (MnO2), which speeds up the reaction, is
bubbled through water and collected in a bottle as shown.

117
The collecting gas over water is based on the assumptions
that the gas does not react with water and it is not completely
soluble in it. These assumptions are valid for O2 gas, but not
for gases such as NH3, which dissolves in water.

 The O2 gas collected in this way is not pure, because

water vapor is also present in the bottle.
 The total gas pressure is equal to the sum of the pressures
exerted by the oxygen gas and the water vapor:

118
 PT = PO2 + PH2O
 When collecting a gas over water, the total pressure is equal to the
atmospheric pressure (Patm = PO2 + PH2O).
Example:
Oxygen gas generated by the decomposition of potassium chlorate is
collected over water. The volume of oxygen collected at 24°C and
atmospheric pressure of 762 mmHg is 128 mL. Calculate the mass (in
grams) of oxygen gas obtained. The pressure of the water vapor at
24°C is 22.4 mmHg. (O = 16)
Solution:
PT = Patm = 762 mmHg ; PH2O = 22.4 mmHg ; PO2 = ?
VO2 = 128 ml/ 1000 = 0.128 L T = 24 + 273 = 297 K m O2 = ?
PT = PO2 + PH2O
PO2 = PT - PH2O = 762 mmHg – 22.4 mmHg = 740 mmHg
740 mmHg
X O2   0.974 atm
760 mmHg

From ideal gas equation: PO2VO2 = nO2 RTO2

119
 PO 2  VO 2 0.974 atm  0128 L
nO    0.00512mol
2
RTO 2 L.atm
0.082  297
K.mol
m
O2
MO 
2
n
O2

(2  16)g
mO  MO  nO   0.00512mol  0.164g
2 2 2
mol

Practice Exercise: Hydrogen gas generated when calcium metal reacts with water is
collected over water. The volume of gas collected at 30°C and pressure of 988 mmHg
is 641 mL. What is the mass (in grams) of the hydrogen gas obtained? The pressure
of water vapor at 30°C is 31.82 mmHg.
Review of Concepts
Each of the color spheres represents a different gas molecule. Calculate the partial
pressures of the gases if the total pressure is 2.6 atm.
120
The Kinetic Molecular Theory of Gases:
o The gas laws help us to predict the behaviour of gases,
but they do not explain why does a gas expand on heating?
o Boltzmann and Maxwell found that the physical
properties of gases can be explained in terms of the motion
of individual molecules.
o The molecular motion is a form of energy, which is
defined as the capacity to do work.
o In mechanics: energy = work done
energy = (force)( distance)
o The SI unit of energy is the joule (J):
1 J = 1 kg m2/s2
1J=1Nm
121
Kinetic energy (KE): is the type of energy used by a
moving object, or energy of motion.
o The kinetic theory of gases treats molecules as hard
spheres without internal structure.

122
The assumptions of kinetic theory of gases:
1. A gas is composed of molecules that are separated from each other by large
distances greater than their own dimensions. The molecules can be considered to be
points; that is, they possess mass but have negligible volume.
2. Gas molecules are in constant motion in random directions, and they frequently
collide with one another. Collisions among molecules are perfectly elastic.
3. Gas molecules exert neither attractive nor repulsive forces on one another.
4. The average kinetic energy of the molecules is proportional to the temperature of
the gas in kelvins. Any two gases at the same temperature will have the same average
kinetic energy: KE =1/2 mu2
Where m is the mass of the molecule and u is its speed. The horizontal bar (--)
denotes an average value. The quantity 𝑢̅ 2 is called mean square speed; it is the
average of the square of the speeds of all the molecules:
2 u12  u 22  .......  u 2N
u 
Where N is the number of molecules. N
KE 𝛼 𝑇
According to the kinetic molecular theory, gas pressure is the result of collisions
between molecules and the walls of their container.
123
124
Distribution of Molecular Speeds:
The kinetic theory of gases enables us to investigate molecular motion
in more detail.
Apparatus for studying molecular speed distribution at a certain
temperature:
The vacuum pump causes the molecules to travel from left to right as
shown (a). (b) The spread of the deposit on the detector gives the
range of molecular speeds, and the density of the deposit is
proportional to the number of molecules moving at different speeds.

125
1) Maxwell speed distribution curves for nitrogen gas at three different
temperatures:
1- The most probable speed: it is the speed of the largest number of molecules.
2- The most probable speed increases as temperature increases (the peak shifts
toward the right)

126
 d) The speed distributions of three gases at the same temperature.

1- Lighter molecules move faster, on average, than heavier ones.

2- The most probable speed decreases as molar mass increases at constant temperature.
127
Root-Mean-Square Speed:
 One way to estimate molecular speed (at any temperature T) is to calculate
the root-mean-square (rms) speed (urms), which is an average molecular
speed.
 From kinetic theory of gases results:
𝐾𝐸 𝑜𝑓 1 𝑚𝑜𝑙= 3/2 𝑅𝑇
𝐾𝐸 𝑜𝑓 1 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 =1/2 𝑚𝑢̅ 2 𝑎𝑛𝑑 1 𝑚𝑜𝑙= 𝑁𝐴𝑥 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
𝑁𝐴(12 𝑚𝑢̅ 2) = 3/2 𝑅𝑇
Where NA is Avogadro’s number and m is the mass of a single molecule.
Because (NAm = ℳ), the above equation can be rearranged to give:
2 3RT
u 
M
Taking the square root of both sides gives:
2 3RT
u  U rms
M
 The root-mean-square speed of a gas increases with the square root of its
temperature (in kelvins).
 Units: R = 8.314 J/K .mol, ℳ = kg/mol, then urms = m/s.
128
Example:
Calculate the root-mean-square speeds of helium atoms and nitrogen
molecules in m/s at 25°C. (He = 4.003 g/mol , N = 14)
Solution:
urms= m/s ? R = 8.314 J/K .mol (1 J = 1 kg m2/s2), the molar mass must
be in kg/mol.
3
MHe  4.003  10 Kg / mol

u rms  3RT  3 (8.314 J/K.mol (298 K)

M 4.00310-3 Kg/ mol

u rms  1.86106 J/Kg

2 2
1 J  1 Kg m / s

u rms  1.86106 Kg m2 / s2 Kg
3
u rms  1.86106 m2 / s2  1.36  10 m/s

129
For N2, the molar mass is 28.02 x 10-3 kg/mol:

u rms  3RT  3 (8.314 J/K.mol (298 K)

M 28.0210-3 Kg/ mol

u rms  2.65105 m2 / s2  515 m/s

Practice Exercise: Calculate the root-mean-square speed of molecular

chlorine in m/s at 20°C.

130
Gas Diffusion and Effusion:
 Gas Diffusion and Effusion are two phenomena based on gaseous
motion.
Gas Diffusion: is the gradual mixing of two gas molecules because of
their kinetic properties.
 A direct determination of gaseous random motion is provided by
diffusion.
 The diffusion process takes a long time to complete. The reason is
that a molecule experiences several collisions while moving from
one place to the other, as shown in Figure

The path travelled by a single gas molecule. Each change in direction

represents a collision with another molecule
131
 Graham’s Law of Diffusion:
Under the same conditions of temperature and pressure, rates of
diffusion for gases are inversely proportional to the square roots of
their molar masses
 Graham observed that molecules with smaller masses diffused
faster than heavy molecules.

Large molecules (slow motion) Small molecules (fast motion)

Mathematically (Graham’s law):

r1

t2
 M2
r2 t1 M1
Where r1 and r2 are the rates of diffusion of gases 1 and 2, t1 and t2 are
the times for effusion for gases 1 and 2 and M1 and M2 are their
molecular masses.
132
Gas Effusion: is a gas escaping through a hole into a vacuum

Diffusion Effusion

 Diffusion always proceeds from a region of higher

concentration to one where the concentration is lower.

133
Example:
A gas made up only of carbon and hydrogen is found to effuse
through a porous barrier in 1.50 min. Under the same
conditions of temperature and pressure, it takes an equal
volume of bromine vapour 4.73 min to effuse through the
same barrier. Calculate the molar mass of the unknown gas,
and suggest what this gas might be. (Br2 = 159.8 g/mol)
Solution:
t1 = 1.5 min, ℳ1 =? t2 = 4.73 min, ℳ2 = 159.8 g/mol

t2
 M2
t1 M1

 4.73 min   159.8 g / mol

 1.5 min 
  M1
134
 By taking square for both sides
t2
 M2
t1 M1
2
 4.73 min   159.8 g / mol
 1.5 min 
  M1
159.8 g / mol
9.94 
M1
159.8 g / mol
M1  16.07 g / mol
9.94
Because the molar masses of C = 12.01 and H = 1.008, the gas is
methane (CH4). (12.01 + 4 x 1.008 = 16.04).

Practice Exercise: It takes 192 s for an unknown gas to effuse through

a porous wall and 84 s for the same volume of N2 gas to effuse at the
same temperature and pressure. What is the molar mass of the
unknown gas? (N = 14).
135
Ideal Gas (Virtual) Real gases (O2, N2, H2)

1. Agree with the assumptions of the Do not agree

kinetic theory of gases

2. Obeys the gas laws under all Obey the gas laws under moderate
conditions of temperature and conditions of temperature and pressure:
pressure. At very low temperature and very high
pressure, the real gases show deviations
from the ideal gas behaviour.

3. The actual volume of molecules is The actual volume of molecules is

negligible considerable
4.No attractive forces between There is attractive forces between
molecules. molecules
5. Molecular collisions are elastic Non elastic collision

136
Chemical Equilibrium

137
Introduction
Equilibrium is a state in which there are no observable changes as time goes by.
When a chemical reaction has reached the equilibrium state, the concentrations of
reactants and products remain constant overtime, and there are no visible changes
in the system.
However, there is much activity at the molecular level because reactant molecules
continue to form product molecules while product molecules react to yield reactant
molecules.
This dynamic situation is the subject of this chapter.

We will discuss:
 Different types of equilibrium reactions
 The meaning of the equilibrium constant and its relationship to the rate constant
 And factors that can disrupt a system at equilibrium.

The concept of Equilibrium and the Equilibrium

Constant
Few chemical reactions proceed in only one direction. Most are reversible.
At the start of a reversible process, the reaction proceeds toward the formation of
products. As soon as some product molecules are formed, the reverse process begins
to take place and reactant molecules are formed from product molecules.
138
Chemical equilibrium is achieved when:
The rates of the forward and reverse reactions are equal
and
The concentrations of the reactants and products remain
constant

Chemical Equilibrium predicts how reaction will proceed and

how far can it go.
Chemical equilibrium does not indicate rates of reactions, just
extent of reaction at equilibrium and how far the reaction is from
equilibrium
Dynamic nature of chemical reaction
aA + bB  cC + dD
A, B decrease with time, C, D increase with time until no
change.

139
Physical equilibrium: Equilibrium between two phases of the same
substance.
The vaporization of water in a closed container at a given
temperature is an example of physical equilibrium. In this instance,
the number of H2O molecules leaving and the number returning to
the liquid phase are equal: H O  H O
2 (l) 2 (g)
 (The double arrow means that the reaction is reversible.)
Chemical equilibrium: Equilibrium between two phases of the different
substance
Note that chemical equilibrium involves different substances as reactants
and products
Dinitrogen tetroxide  nitrog
N O g   2NO (g)
2 4 2
Colorless gas  dark brown color gas

Liquid water in equilibrium with its vapor at room temperature

140
Chemists are particularly interested in chemical equilibrium processes, such
as the reversible reaction involving nitrogen dioxide (NO2) and dinitrogen
tetroxide (N2O4) (Figure 14.1).
The progress of the reaction can be monitored easily because N2O4 is a
colorless gas, whereas NO2 has a dark brown color that makes it sometimes
visible in polluted air.
Suppose that N2O4 is injected into an evacuated flask. Some brown
color appears immediately, indicating the formation of NO2 molecules.
The color intensifies as the dissociation of N2O4 continues until
eventually equilibrium is reached.
Beyond that point, no further change in color is evident because the
concentrations of both N2O4 and NO2 remain constant.

FIGURE 14.1 A reversible reaction between N2O4 and NO2 molecules

NO2 and NO2 to N2O4 are still going on. We do not see a color change because
the two rates are equal the removal of NO2 molecules takes place as fast as the
production of NO2 molecules, and N2O4 molecules are formed as quickly as
they dissociate. Figure 14.2 summarizes these three situations.
141
Figure 14.2 N2O4 (g) 2NO2 (g)

equilibrium
equilibrium
equilibrium

(a) (b) (c)

Start with NO2 Start with N2O4 Start with NO2 &
N2O4

Change in the concentrations of NO2 and N2O4 with the time, in three situation.
(a) Initially only NO2 is present.
(b) Initially only N2O4 is present.
(c) Initially a mixture of NO2 and N2O4 is present.
Note that even though equilibrium is reached in all cases, the equilibrium
concentration of NO2 and N2O4 are not the same
142
 moles of solute
Equilibrium Constant: Table 14.1 shows some data for the M = liters of solution

N2O4 (g) 2NO2 (g)

The gas concentrations are expressed in morality,

The ratio [NO2] / [N2O4] gives scattered values, the ratio [NO2]2 /
[N2O4] gives a nearly constant value that averages 4.63 × 10-3:
constant

143
 N2O4 (g) 2NO2 (g)
[NO2]2
K= = 4.63 x 10-3
[N2O4]
Where K is the equilibrium constant

aA + bB cC + dD
Law of Mass Action

for a reversible reaction at equilibrium and a constant temperature, a certain

ratio of reaction and product concentrations has a constant value, K

[C]c[D]d
K=
[A]a[B]b
Equilibrium Will
K >> 1 Lie to the right Favor products
K << 1 Lie to the left Favor reactants

144
 Homogenous equilibrium applies to reactions in which all reacting species are
in the same phase.
N2O4 (g) 2NO2 (g)
[NO2]2
Kc =
[N2O4]
Not that the subscript in Kc indicates that the concentration of the reaction species
are expressed in molarity or moles per liter.

The concentrations of reactants and products in gaseous reaction can also be

expressed in terms of their partial pressures.
N2O4 (g) 2NO2 (g)
We can write 2
PNO
Kp = 2

PN2O4
Where PNO2 and PN2O4 are the equilibrium partial pressures (in atm). The
subscript in KP tells us that equilibrium concentrations are expressed in terms of
pressure.

145
In general , Kc is not equal to Kp, since the partial pressures of reactants and
products are not equal to their concentrations expressed in moles per liter.
A simple relationship between Kp and Kc can be derived as follows. Let us
consider the following equilibrium in the gas phase:
aA(g)  bB(g)
Where a and b are stoichiometric coefficients. The equilibrium constant Kc is

given by b
[B]
Kc  a
[A]
b
PB
KP  a
and the expression for Kp is PA

Where PA and PB are the partial pressures of A and B.

146
 aA(g)  bB(g)

Where PA and PB are the partial pressure of A and B. Assuming ideal gas behavior.

PA  A a RT , PB  B b RT
n RT
A
P V n RT  P 
A A A V
n RT
B
P V n RT  P 
B B B V
n
 concentration    mole/L 
V
substituting these relation into the expression for K , we obtain
P
b b
 nB RT   nB 
   
 V   V 
KP   RT b a
a a
 n A RT   nA 
   
 V   V 

147
Now both nA/V and nB/V have units of mol/L and can be replaced by [A], [B], so that

b
KP 
B
RT b a
a
A 
Δn
KP  Kc RT 

where

Δn  b  a

Δn  moles of gaseous product  moles of gaseous reactants

148
 ∆n = moles of gaseous products – moles of gaseous reactants
Where
∆n = (c + d) – (a + b)
∆n = b – a
Since pressure are usually expressed in atm, the gas constant R is given by
0.0821 L.atm/K.mol, and we can write the relationship between Kp and Kc as
Δn
K P  K c (0.08217T)

To use this equation, the pressures in KP, must be in atm.

In general, KP ≠ KC except in the special case in whish ∆n = 0 as in the equilibrium
mixture of molecular hydrogen, molecular bromine, and hydrogen bromide:

H2 (g) + Br2 (g) 2HBr (g)

In this case, Equitation can be written as

K P  K c (0.08217T)Δn
0
K P  K c (0.08217T)

Any number raised to the zero power is equal to 1.

K P  Kc  1

K P  Kc 149
As another example of homogeneous equilibrium, let us consider the ionization of
acetic acid (CH3COOH) in water:

CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)

[CH COO -][H O+]
The equilibrium constant is Kc = ‘ 3 3 [H2O] = constant
[CH3COOH][H2O]
In 1 L, or 1000g, of water, there are 1000g/(18.02 g/mol), or 55.5 moles, of
water. Therefore, the “concentration” of water, or [H2O], is 55.5 mol/L or 55.5 M.
This is the large quantity compared to the concentration of other species in
solution (usually 1 M or smaller), and we can assume that it is does not change
appreciably during the course of a reaction. Thus we may treat [H2O] as a
constant and rewrite the equilibrium constant as

Kc =
[CH3COO-][H3O+ ]
[CH3COOH]

Kc = Kc‘[H2O]

General practice not to include units for the equilibrium

constant.

150
Example : Write expressions for KC, and KP if applicable, for the following reversible
reactions at equilibrium :
(a) HF (aq) + H2O (l) H3O+ (aq) + F- (aq)
(a) 2NO (g) + O2 (g) 2NO2 (g)
(b) CH3COOH (aq) + C2H5OH (aq) CH3COOC2H5 (aq) + H2O(l)

Reasoning and Solution: keep in mind the following facts:

(1) The KP expression applies only to gaseous reactions and
(2) The concentration of solvent (usually water) does not appear in the equilibrium
constant expression.
(a) Because there are no gases present, Kp does not apply and we have only
KC  -
' [H O ][F ]
3
KC 
[HF][H 2 O]

HF is a weak acid , so that the amount of water consumed in acid ionizations is

negligible compared with the total amount of water present as solvent. Thus we
 -
can rewrite the equilibrium constant as [H 3 O ][F ]
KC 
[HF]

151
 2 2
(b) [NO 2 ] PNO
2
KC  2 and KP  2
[NO] [O 2 ] PNO PO
2 2

(C) The equilibrium constantK C' is given by

' [H 3 COOC2 H 5 ][H 2 O]
KC 
[H 3 COOH][C 2 H 5 OH]

Because the water produced in the reaction is negligible compared with the water
solvent, the concentration of water does not change. Thus we can write the new
equilibrium constant as [H 3 COOC2 H 5 ]
KC 
[H 3 COOH][C 2 H 5 OH]

Practice Exercise : write KC and KP for the decomposition of nitrogen pentoxide:

2N2O5 (g) 4NO2 (g) + O2 (g

152
Example: The following equilibrium process has been studied at 230 oC:
2NO (g) + O2 (g) 2NO2 (g)
In one experiment the concentrations of the reacting species at equilibrium are found
to be [NO] = 0.0542 M, [O2] = 0.127M, and [NO2] = 15.5 M. calculate the equilibrium
constant (KC) of the reaction at this temperature.

Reasoning and Solution: The equilibrium constant is given

[NO2]2 (15.5)2
=
[NO]2[O2] (0.0542)2(0.127)

Comment: Note that KC is given without units. Also, the large magnitude of KC is
Kc high
consistent with the = 6.44
= product (NO2) concentration relative to the × 105
concentrations of
the reactants (NO and O2)

153
 Practice Exercise : Carbonyl chloride (COCl2), also called phosgene, was
used in World War I as a poisonous gas. The equilibrium concentrations for
the reaction between carbon monoxide and molecular chlorine to form
carbonyl chloride
CO (g) + Cl2 (g) COCl2 (g)

At 74 oC are [CO] = 1.2 × 10-2 M , [Cl2] = 0.054 M, and [COCl2] = 0.14 M.

calculate the equilibrium constant (KC) .

Reasoning and Solution:

The equilibrium concentrations for the reaction between carbon monoxide and
molecular chlorine to form COCl2 (g) at 740C are [CO] = 0.012 M, [Cl2] = 0.054
M, and [COCl2] = 0.14 M. Calculate the equilibrium constants Kc and Kp.
[COCl2] 0.14
Kc = = = 216
[CO][Cl2] 0.012 x 0.054
Kp = Kc(RT)Δn Δn = 1 – 2 = -1 And R = 0.0821 and T = 273 + 74 = 347 K

  1
KC 216
K p  K C RT  Kp    7.6
RT 0.0821347 

154
Example: The equilibrium concentration KP for the decomposition of
phosphorus pentachloride to phosphorus trichloride and molecular chlorine
PCl5 (g) PCl3 (g) + Cl2 (g)

is found to be 1.05 at 250 oC. If equilibrium partial pressures of PCl5 and PCl3 are
0.875 atm and 0.463 atm , respectively, what is the equilibrium partial pressure of Cl2 at
250 oC?
Reasoning and Solution : first, we write KP in terms of the partial pressures of
the reacting species.
P P
Knowing the partial pressures, we write K P  PCl3 Cl 2
PPCl5
0.463 P 
1.05  Cl 2

0.875 

or PCl 2  1.05  0.875   1.98atm

0.463
Comment : Notes that we have added as the unit for PCl2

155
Practice Exercise The equilibrium constant Kp for the reaction
2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure of O2 if the PNO = 0.400 atm
and PNO2 = 0.270 atm?

Solution : 2
PNO PO
2
K  2
P PNO
2
2
PNO
2
PO  K
2 P P2
NO

0.400 2
PO  158   347 atm
2
0.270 2

156
Example : The equilibrium constant KC for the reaction
N2O4 (g) 2NO2 (g)

is 4.63 × 10-3 at 25 oC. What is the value of KP at this temperature?

Reasoning and Solution : The relationship between KC and KP is given by

Equation
Δn
K P  K c (0.08217T)

Because T = 298 K and ∆n = 2 – 1 = 1 , we have

3
K P  (4.63  10 )(0.0821  298)  0.113

Comment : not that KP, like KC, is a dimensionless quantity. This example shows
that we can get quite a different value for the equilibrium constant for the same
reaction, depending on whether we express the concentrations in moles per liter or
in atmospheres.

157
Practice Exercise : For the reaction

N2 (g) + 3 H2 (g) 2NH3 (g)

PP is 4.3 × 10-4 at 375 oC. Calculate KC for the reaction.

158
Heterogeneous equilibrium result from a reversible reaction involving reactants
and products that are in different phases.

For example, when calcium carbonate is heated in closed vessel, the following
equilibrium is attained:

CaCO3 (s) CaO (s) + CO2 (g)

Figure 14.3 In (a) and (b) the equilibrium pressure of CO2 is the same at same temperature,
despite the presence of different amounts of CaCO3 and CaO.
PCO 2 = Kp
PCO2 does not depend on the amount of CaCO3 or CaO

159
The two solid and one gas constitute three separate phases. At equilibrium,
we might write the equilibrium constant as
[CaO][CO2]
Kc‘=
[CaCO3]
For example, when calcium carbonate is heated in closed vessel, the
following equilibrium is attained:

The “concentration” of the solid , like its density, is an intensive property and does
not depend on how much of the substance is present. For this reason, the terms [
CaCO3] and [CaO] are themselves constants and can be combined with the
equilibrium constant.
[CaCO3] [CaCO3] = constant
K‘c = Kc = [CO2] [CaO] = constant
[CaO]

Note that value of KC does not depend on how much CaCO3 and CaO are
present, as long as some of each is present at equilibrium .

Alternatively , we can express the equilibrium as Kp = PCO

2

160
Example : Write the equilibrium constant expression KC and Kp if applicable, for
each of the following heterogeneous system:
(a) (NH4)2Se (s) 2NH3 (g) + H2Se (g)
(b) AgCl (s) Ag+ (aq) + Cl- (aq)
(c) P4 (s) + 6 Cl2 (g) 4PCl3 (l)

Reasoning and Solution : Note that the concentrations of solids and liquids do
not appear in the equilibrium constant expressing.
(a) The equilibrium constant is given by
,K = [NH3]2[H2Se]
c [(NH4)2Se ]
However, since (NH4)2Se is a sold, we write the new equilibrium constant as
Kc= [NH3]2[H2Se]

Where KC = K , C [(NH4)2Se ]. Alternatively, we can express the equilibrium constant

KP in terms of the partial pressure of NH3 and H2Se
2
Kp = PNH3 PH2Se
161
(b) The equilibrium constant is

,= [Ag+] [Cl -]
KC
[(AgCl ]

KC = [Ag +] [Cl -]

Again, we have incorporated [AgCl] into KC because AgCl is a solid.

,= [PCl3]4
(c) The equilibrium constant is KC
[P4][Cl2]6
Because pure solids and pure liquids do not appear in the equilibrium constant
expression, we write , 1
Kc= [Cl ]6
2

Alternatively, we can express the equilibrium constant in terms of the pressure

of Cl2:
1
KP = P6Cl2
162
Prectice Exercies : Write
the equilibrium constant expression KC and Kp
for formation of nickel tetracarbonyl, which is used to separate nickel
from other impurities:
Ni(s) + 4CO (g) Ni (CO)4 (g)

163
Example : Consider the following heterogeneous equilibrium :
CaCO3 (s) CaO (s) + CO2 (g)

At 800 oC the pressure of CO2 is 0.236 atm. Calculate

(a) Kp and (b) Kc for the reaction at this temperature

Reasoning and Solution :

(a) Because the concentration of the solid (CaCO3) does not appear in the
equilibrium constant expression, using Equation
Kp = PCO
2

KP = 0.236

(b) From equation K P  K c (0.08217T)Δn

In this case. T = 800 + 273 = 1073 K and ∆n = 1

so we substitute these in the equation and obtain
0.236 = Kc (0.0821 x 1073)
KC = 2.68 x 10-3

164
Practice Exercies :
Consider the following equilibrium at 295 K:
NH4HS (s) NH3 (g) + H2S (g)
The partial pressure of each gas is 0.265 atm. Calculate Kp and Kc for the
reaction?

Kp = P P = 0.265 x 0.265 = 0.0702

NH3 H2S
Kp = Kc(RT)∆n

Kc = Kp(RT)
- ∆n

∆n = 2 – 0 = 2 and T = 295 K
Kc = 0.0702 x (0.0821 x 295)-2 = 1.20 x 10-4

165
 [C][D] [E][F]
A+B C+D Kc‘ Kc‘ = Kc‘‘=
[A][B] [C][D]
C+D E+F Kc‘‘
[E][F]
A+B E+F Kc Kc =
[A][B]

Kc = Kc‘ x Kc‘‘

If a reaction can be expressed as the sum of two

or more reactions, the equilibrium constant for
the overall reaction is given by the
__________________ of the equilibrium
constants of the individual reactions.

15.2

166
Multiple Equilibria : The reactions we have considered so far are all relatively
simple. A more complicated situation is one in which the product molecules in
one equilibrium system are involved in a second equilibrium process:
A+ B C+D
C+D E+F

The products formed in the first reaction, C and D, react further to form
products E and F. At equilibrium we can write two separate equilibrium
constants:
‘ [C][D]
Kc =
[A][B]

And [E][F]
Kc‘‘=
[C][D]

167
 [C][D] [E][F]
A+B C+D Kc‘ Kc‘ = Kc‘‘=
[A][B] [C][D]
C+D E+F Kc‘‘
[E][F]
A+B E+F Kc Kc =
[A][B]

Kc = Kc‘ x Kc‘‘

If a reaction can be expressed as the sum of two

or more reactions, the equilibrium constant for
the overall reaction is given by the
__________________ of the equilibrium
constants of the individual reactions.

15.2

168
 A+B C+D Kc‘
C+D E+F Kc‘‘
Overall reaction: A+B E+F Kc
and the equilibrium constant Kc for the overall reaction is
[E][F]
Kc =
[A][B]
We obtain the same expression if we take the product of the expressions for K′C
and K ″C: K' K'' 
[C][D]

[E][F]

[E][F]
C C [A][B] [C][D] [A][B]

We can now make an important statement about multiple Equilibria: If

a reaction can be expressed as the sum of two or more reactions, the
equilibrium constant for the overall reaction is given by the product of
the equilibrium constants of the individual reactions.
Kc = Kc‘ x Kc‘‘
169
Among the many known examples of multiple Equilibria is the ionization of
diprotic acids in aqueous solution . The following equilibrium constants have
been determined for carbonic acid (H2CO3) at 25 oC:
 
  , [H ][HCO 3 ] 7
H 2 CO 3 (aq)  H (aq)  HCO 3 (aq) KC   4.2  10
[H 2 CO 3 ]
 2
[H ][CO 3 ] 11
HCO3- (aq)  H  (aq)  CO32  (aq)
"
KC  -
 4.8  10
[HCO ]
3
 2 2
 2 [H ] [CO 3 ]
H 2 CO 3 (aq)  2H (aq)  CO 3 (aq) KC 
[H 2 CO 3 ]

And the corresponding equilibrium constant is given by

Using Equation

Kc = Kc ‘ x Kc ‘‘ = (4.2 ×10-7 )(4.8 × 10-11) = 2.0 × 10-17

170
 N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)

[NO2]2 [N2O4] 1
K= = 4.63 x 10-3 K‘= = = 216
[N2O4] [NO2]2 K

When the equation for a reversible reaction is written in the

opposite direction, the equilibrium constant becomes the
____________________ of the original equilibrium constant.

15.2

171
The form of K and the Equilibrium Equation

Before concluding this section. Let us look at two important rules for writing
equilibrium constant :
When the equation for a reversible reaction is written in the opposite
direction, the equilibrium constant becomes the reciprocal of the original
equilibrium constant. Thus if we write the NO2 – N2O4 equilibrium as

N2O4 (g) 2NO2 (g)

then
[NO ] 2
K  2  4.63  10 - 3
C [N O ]
2 4

However, we can represent the equilibrium equally well as

2NO2 (g)  N2O4 (g)
and the equilibrium constant is now given by
[N O ]
K'  2 4  1  1
 216
C 2 - 3
C 4.63  10
[NO ] K
2

172
And the equilibrium constant is now given by
' [N 2 O 4 ] 1 1
KC     216
[NO 2 ]
2 kc 4.63  10  3

You can see the KC = 1/ K’C or KC K’C= 1.00. ether KC or K’C is a valid equilibrium
constant., but it is meaningless to say that equilibrium constant for the NO2 – N2O4 is
4.63 × 10-3 , or 216, unless we also specify how the equilibrium equation is written.

 The value of K also depends on how the equilibrium equation is balanced.

Consider the following way of describing the same equilibrium :
' [NO2]
½N2O4 (g NO2 (g) KC 
)
[N2O4]½

N2O4 (g) 2NO2 (g) [NO2]2

KC 
[N2O4]

173
Looking at the exponent we see that K’C = K C in Table
14.1 we find KC = 4.63 × 10-3 ; therefore K’C = 0.0680

According to the law of mass action, each concentration term

in the equilibrium constant expression is raised to a power
equal to its stoichiometric coefficient. Thus if you double a
chemical equation throughout, the corresponding equilibrium
constant will be the square of the original value; if you triple
the equation, the equilibrium constant will be cube of the
original value, and so on. The NO2 – N2O4 example illustrates
once again the need to write the chemical equation when
quoting the numerical value of an equilibrium constant.

174
The following example deals with the relationship between the equilibrium
consents for differently balanced equations describing the same reaction

Example : The reaction for the production of ammonia can be written in a

number of ways:

( a )N 2 ( g )  3H 2 ( g )  2 NH 3 ( g )
3
( b ) N 2 ( g )  H 2 ( g )  NH 3 ( g )
1
2 2
2
( c ) N 2 ( g )  H 2 ( g )  NH 3 ( g )
1
3 3

Write the equilibrium constant expression for each formulation. (express the
concentrations of the reacting species in mol/L)
(d) How are the equilibrium constants related to one another?

175
Reasoning and Solution: Remember that the equilibrium constant expression
depends on how the equation is balanced; that is, the stoichiometric coefficients
used in the equation.

: [ NH 3 ] 2
( a )K a 
[ N 2 ][ H 2 ] 3
[ NH 3 ]
( b )K b  1 3
2 2
[ N2 ] [ H 2 ]
2
3
[ NH 3 ]
( c )K c  1
[ N2 ] 3 [ H 2 ]
( d ) K a  K b2
K a  K c3
3
K a  K or K b  K c 2
2 3
c
176
 Summary of guideline for Writing Equilibrium Constant Expressions

• The concentrations of the reacting species in the condensed phase are expressed in mole/L
(M). In the gaseous phase, the concentrations can be expressed in mole/L (M) or in atm.
• The concentrations of pure solids, pure liquids and solvents do not appear in the equilibrium
constant expressions.
• The equilibrium constant (KC or KP ) is a dimensionless quantity.
• In quoting a value for the equilibrium constant, we must specify the balanced equation and the
temperature.
• If a reaction can be expressed as a sum of two or more reactions, the equilibrium constant for
the overall reaction is given by the product of the equilibrium constants of the individual
reactions.

177
 The Relationship between Chemical Kinetics and Chemical Equilibrium
Let us suppose that the following reversible reaction occurs via a mechanism consisting of a
single elementary step in both the forward and reverse direction:
kf
A + 2B AB2 Since both kf and Kr are
kr constants at given
The forward rate is given by temperature, their ratio is
rate f = kf [A][B]2
also a constant, which equal
And the reverse rate is given by to the equilibrium constant KC
rater = kr [AB2]
Where Kf and Kr are the rate constants for the forward and reverse directions. At equilibrium,
when no net changes occur, the two rates must be equal :
rate f = rate r
OR
kf [A][B]2 = kr [AB2]
kf [AB2]
=
kr [A][B]2

178
Since both Kf and Kr are constants at given temperature, their ratio is also a
constant, which equal to the equilibrium constant KC

kf [AB2]
= Kc=
kr [A][B]2

179
 The reaction quotient (Qc) is calculated by substituting the initial
concentrations of the reactants and products into the equilibrium
constant (Kc) expression.
IF
• Qc > Kc system proceeds from right to left to reach equilibrium
• Qc = Kc the system is at equilibrium
• Qc < Kc system proceeds from left to right to reach equilibrium

180
 Calculating Equilibrium Concentrations

1. Express the equilibrium concentrations of all species in terms

of the initial concentrations and a single unknown x, which
represents the change in concentration.
2. Write the equilibrium constant expression in terms of the
equilibrium concentrations. Knowing the value of the
equilibrium constant, solve for x.
3. Having solved for x, calculate the equilibrium concentrations
of all species.

181
At 12800C the equilibrium constant (Kc) for the reaction
Br2 (g) 2Br (g)

Is 1.1 x 10-3. If the initial concentrations are [Br2] = 0.063 M and [Br] =
0.012 M, calculate the concentrations of these species at equilibrium.

Let x be the change in concentration of Br2

Br2 (g) 2Br (g)
Initial (M) 0.063 0.012
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x

[Br]2 (0.012 + 2x)2 Solve for x

Kc = Kc = = 1.1 x 10-3
[Br2] 0.063 - x
15.4

182
 (0.012 + 2x)2
Kc = = 1.1 x 10-3
0.063 - x
4x2 + 0.048x + 0.000144 = 0.0000693 – 0.0011x
4x2 + 0.0491x + 0.0000747 = 0
2
ax + bx + c =0 x=
-b ± b2 – 4ac
2a
x = -0.0105 x = -0.00178
Br2 (g) 2Br (g)
Initial (M) 0.063 0.012
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x
At equilibrium, [Br] = 0.012 + 2x = -0.009 M or 0.00844 M
At equilibrium, [Br2] = 0.062 – x = 0.0648 M
15.4

183
 _______________________________
If an external stress is applied to a system at equilibrium, the system
adjusts in such a way that the stress is partially offset as the system
reaches a new equilibrium position.

• Changes in Concentration

N2 (g) + 3H2 (g) 2NH3 (g)

Equilibrium
Add
shifts left to
NH3
offset stress

15.5

184
 Le Châtelier’s Principle
• Changes in Concentration continued
Remove Add Add Remove

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left

185
 Le Châtelier’s Principle
• Changes in Volume and Pressure
A (g) + B (g) C (g)

Change Shifts the Equilibrium

Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas

186
 Le Châtelier’s Principle
• Changes in Temperature

Change Exothermic Rx Endothermic Rx

Increase temperature K decreases K increases
Decrease temperature K increases K decreases

colder hotter

187
 Le Châtelier’s Principle
• Adding a Catalyst
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner

uncatalyzed catalyzed

Catalyst lowers Ea for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift equilibrium.

188
 Le Châtelier’s Principle

Change Equilibrium
Change Shift Equilibrium Constant
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no

189
Thermochemistry

190
 Thermochemistry
2011-2012

University of Benghazi
Faculty of Science
Chemistry Department
For Premedical Students

Dr. Mohamed Fadel

191
 Thermochemistry

THE NATURE OF ENERGY AND TYPES OF ENERGY

ENERGY CHANGES IN CHEMICAL REACTIONS
ENTHALPY
CALORIMETRY
STANDARD ENTHALPY OF FORMATION AND REACTION
HEAT OF SOLUTION AND DILUTION

192
 General Review
Objectives

After studying this review, a student will be expected to be able to:

1. Explain the difference between an open, closed and isolated system.
2. Calculate the amount of heat energy, q, absorbed or released when heating or
cooling an object or substance by specific amount (∆T).
3. Determine if a reaction is endothermic or exothermic and assign the correct
sign (+ or -) to q.
4. Define thermal equilibrium and, given the application information, calculate
the T, when tow objects or substances arrive at thermal equilibrium.
5. Define the following terms and include the applicable units:
a) Heat capacity
b) Specific heat capacity
c) Molar heat capacity
d) Latent heat

193
 General Review

6. For a given example, identify the system and surroundings. In addition,

calculate: Heat capacity
a) q for heating or cooling
b) q for phase change

194
Introduction
Every chemical reaction obeys two fundamental laws:

 Law of conservation of mass: energy can be neither destroyed nor created .

 Law of conservation of energy: the total quantity of energy in the universe
is assumed constant
In this chapter we will look at the energy changes that accompany chemical
reaction.
Thermochemistry: is the study of heat change in chemical reaction.
Thermodynamics: is the study of the energy involved in physical and
chemical processes.
physical processes: include t he heating and cooling of substances, phase
change, and changes in physical parameters such as the volume and
pressure of the gas.
Chemical processes :often involve chemical reactions and associated heat
flow.

Thermochemistry is branch of thermodynamics that investigates the heat flow that

occurs during these reactions.
In this topic, some of the basic concepts of the thermodynamics such as:
 Heat capacity
 Specific heat
 Latent heat will be reviewed.
195
 THE NATURE OF ENERGY AND TYPES OF ENERGY
Energy and Work

Energy: is defined as the capacity to do work. We defined work as “force × distance

“ . and Chemists define work as directed energy change resulting from a process.
there are many different types of energy, such as:

 Rsdiant energy, or solar energy, comes from the sun and Earth’s primary
energy source.
 Heat energy, which is the energy transferred from or to the system due to
temperature changes.
 Kinetic energy, which is the energy of the objects due the motion.
 Thermal energy, is the energy associated with the random motion of atoms and
molecules.
 Chemical energy, is the energy stored within the bonds of chemical
substances.
 Nuclear energy, is the energy stored within the collection of neutrons and
protons in the atom.
 Electrical energy, is the energy associated with the flow of electrons.
 Potential energy, is the energy available by virtue of an object’s position
196
Units of Energy
The SI unit of heat (or energy of any form) is the Joule.

ENERGY CHANGES IN CHEMICAL REACTIONS

Almost all-chemical reaction absorbs or produces (release) energy, generally in

the form of heat. It is important to understand the distinction between heat and
thermal energy.
 Heat: is the transfer of chemical energy between two bodies that are at
different temperature. Thus we often speak of the “heat flow” from a hot
object to cold one. Although the term “heat” by itself implies the transfer of
energy, we customarily talk of “heat absorbed” or “heat released”. When
describing the energy changes that occur during a process.

197
 In order to analyze energy change associated with chemical reaction we must first
define the system, or the specific part of the universe that is of interest to us

System and Surroundings

In any study of heat flow, it is important to make a distinction between a system
and its surroundings.
A system: is the part of universe that one wants to study.
For example, when a chemical reaction takes place, chemists consider the
reactions to be system.
The surroundings: are the rest of the universes outside the system.
During a reaction, the surroundings would be the vessels (flasks, test tubes, etc.)
where the reaction took place, including the air and surroundings thus constitute
the universe.
Depending on the interactions between a system and its surroundings, there are
three common system types defined in chemistry:
An open system: can exchange both matter and energy with its surroundings.
A closed system: can exchange only energy but not matter with its surroundings.
An isolated system: can exchange neither matter nor energy with its
surroundings.
198
An open system,
which allows the A closed system, an isolated system,
exchange of both which allows the which allows neither
energy and mass exchange of energy energy nor mass to be
with surroundings; but not mass; and

199
ENTHALPY
Most physical and chemical changes, including those that take place in living systems, occur in
the constant-pressure conditions of our atmosphere.
 In the laboratory, for example, reactions are generally carried out in beakers, flasks, or test
tubes that remain open to their surroundings and hence to a pressure of approximately one
atmosphere (1 atm).
To quantify the heat flow into or out of a system in a constant-pressure process,
chemists use a property called enthalpy, represented by the symbol H and defined as E+PV.
 Enthalpy is an extensive property; its magnitude depends on the amount of the substance
present.
It is impossible to determine the enthalpy of a substance, so it is the change in enthalpy, ∆H
that we actually measure. (The Greek letter delta, ∆, symbolizes change)


200
 (a) (b)
(a) An exothermic process.
(b) An endothermic process. Parts
 (a) and (b) are not dawn to the same scale; that is, the heat released in the formation of H2O form H2
and O2 is not equal to the heat absorbed in the decomposition of HgO

201
The enthalpy of reaction, ∆H, is the difference between the enthalpies of the
products and the enthalpies of the reactants:

∆H = H (products) - H (reactants) (6.1)

In other words, ∆H represents the heat given off or absorbed during a

reaction. The enthalpy of reaction can be positive or negative, depending on
the process.

For an endothermic process (heat absorbed by the system from the

surroundings), ∆H is positive (that is, ∆H > 0).

For an exothermic process (heat released by the system to the

surroundings), ∆H is negative (that is, ∆H < 0).

202
 An Exothermic process (q < 0), in which heat flows from the
reaction system into the surroundings.
A +B  AB + heat
2H2 (g) + O2 (g)  2H2O (l) + energy
q<0
H2O (g)  H2O (l) + energy

An Endothermic process (q > 0), in which heat flows from the
surroundings into the reaction system.
A +B+ heat  AB
2HgO (s) +Energy y  2Hg (l) + O2 (g)
q>0
H2O (s) + Energy  H2O (l)

203
 THE RMOCHEMICAL EQUATIONS
 At 0°C and a pressure of 1 atm, ice melts to form liquid water.
 Measurements show that for every mole of ice converted to liquid water under these
conditions, 6.01 kilojoules (kJ) of energy are absorbed by the system (ice).
 Since ∆H is a positive value, this is an endothermic process, as expected for an energy-
absorbing change of melting ice (Figure 6.4). The equation for this physical change is

FIGURE 6.4
Melting 1 mole of ice at 0°C
(an endothermic process)
results in an enthalpy
increase in the system of 6.01
k J.

H2O(s)  H2O (l) ∆H = 6.01 kJ

204
As another example, consider the combustion of methane (CH4), the principal
component of natural gas:

CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) ΔH= - 890.4 kJ

FIGURE 6.5
Burning 1 mole of methane in oxygen
gas (an exothermic process) results in
an enthalpy decrease in the system of
890.4 k J.

205
From experience we know that burning natural gas releases heat to its surroundings, so it
is an exothermic process, and ΔH must have a negative value. This enthalpy change is
represented in Figure 6.5.
The equations for the melting of ice and the combustion of methane are examples of
thermochemical equations, which show the enthalpy changes as well as the mass
relationships.

The following guidelines are helpful in writing and interpreting thermochemical equations:
 The stoichiometric coefficients always refer to the number of moles of a substance.
Thus, the equation for the melting of ice may be “read” as follows:
When 1 mole of liquid water is formed from 1 mole of ice at 0°C, the enthalpy change
is 6.01 kJ.
For the combustion of methane, we interpret the equation this way:
 When 1 mole of gaseous methane reacts with 2 moles of gaseous oxygen to form 1
mole of gaseous carbon dioxide and 2 moles of liquid water, the enthalpy change is -
890.4 kJ.

 When we reverse an equation, we change the roles of reactants and products.

Consequently, the magnitude of ΔH for the equation remains the same, but its sign
changes. For example, if a reaction consumes thermal energy from its surroundings

206
(that is, if it is endothermic), then the reverse reaction must
release thermal energy back to its surroundings (that is, it must be exothermic) and
The enthalpy change expression must also change its sign. Thus, reversing the melting of ice and
the combustion of methane, the thermochemical equations are

H2O(s)  H2O (l) ∆H = 6.01 kJ

H2O (l) → H2O(s) ΔH= - 6.01 kJ

CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) ΔH= - 890.4 kJ
CO2 (g) + 2H2O (l) → CH4 (g) + 2O2 (g) ΔH = 890.4 kJ
and what was an endothermic process becomes exothermic, and vice versa.
 If we multiply both sides of a thermochemical equation by a factor n, then ΔH must also change
by the same factor. Thus, for the melting of ice, if n = 2, then

2H2O(s) → 2H2O (l) ΔH = 2(6.01 kJ) = 12.0 kJ

 When writing thermochemical equations, we must always specify the physical states of all
reactants and products, because they help determine the actual enthalpy changes. For example, in
the equation for the combustion of methane, if we show water vapor rather than liquid water as a
product,

207
 CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g) ΔH = - 802.4 kJ
the enthalpy change is -802.4 kJ rather than -890.4 kJ because 88.0 kJ
are needed to convert 2 moles of liquid water to water vapor; that is,

2H2O (l) → 2H2O (g) ΔH = 88.0 kJ

208
EXAMPLE
Given the thermochemical equation

SO2 (g) + ½ O2 (g) SO3 (g) ∆H = - 99.1 kJ

Calculate the heat evolved when 74.6 g of SO2 (molar mass = 64.07 g/mol) is converted to SO3.
Answer : The thermochemical equation shows that for every mole of SO2 burned, 99.1 kJ of
heat are given off (note the negative sign). Therefore, the heat produced when 74.6 g of SO2
reacts is
1 mol SO
74.6 g SO  2   99.1kJ  - 115 kJ
2 64.07g SO 1 mol SO
2 2
PRACTICE EXERCISE
Calculate the heat evolved when 266 g of white phosphorus (P4) burn in air according
to the equation
P4(s) + 5O2 (g)  P4O10 (s) ∆H = - 3013 kJ

209
CALORIMETRY
In the laboratory heat changes in physical and chemical processes are measured with a
calorimeter, a closed container designed specifically for this purpose. Our discussion of
calorimeter, the measurement of heat changes, will depend on an understanding of specific heat
and heat capacity, and so let us consider them first.

Specific Heat and Heat Capacity:

The terms heat capacity and specific heat are both a measure of how many Joules are required
to heat something up by one degree. Why are there two different terms to describe this?

Specific heat (s) of a substance: is the amount of heat required to raise the temperature of one
gram of the substance by one degree and has units of Joules per gram per degree. Specific heat
is usually represented by the symbol c. for a pure substance of mass m, the expression for q is
written as:

q = m  s  T

Where m is the mass of the sample and ∆t is the temperature change:

The temperature change is the difference between the final temperature (Tf) and the initial
temperature (Ti).

∆t = tfinal - tinitial

210
Heat capacity (C) : is usually used for objects, like a piece of apparatus
used in an experiment. The heat capacity (C) of a substance is the
amount of heat required to raise the temperature of a given quantity
of the substance by one degree Celsius. The units of heat capacity are
Joules per degree and are represented by the symbol C. In a chemical
reaction, the relationship between the amount of heat q an object’s heat
capacity C, and the temperature change ∆T is:
q = C × ∆T
Specific heat is an intensive property, whereas heat capacity is an
extensive property.

The relationship between the heat capacity and specific heat of a

substance is
C = ms
where m is the mass of the substance in grams. For example, the specific
heat of water
is 4.184 J/g °C, and the heat capacity of 60.0 g of water is
(60.0 g)(4.184 J/g °C) 251 J/°C
Units of Energy The SI unit of heat (or energy of any form) is the Joule.
211
Units of Temperature:
For most reaction involving heat, a temperature difference is
calculated:
∆T = Tfinal - Tinitial

And the unit for temperature most often in chemistry is Kelvin. If

the initial temperature of a substance is 25.0 oC and the final
temperature is 35.3 oC, then the difference , ∆T, is 10.3 oC. For the
same example, the initial temperature of the substance is 298.2
K, the final temperature is 308.5 K, and ∆T is 10.3 K. The
temperature differences are used in heat calculation, either scale
is acceptable. Do not calculate a difference in Celsius and then
add 273 oC to “convert” to K!

212
Example:
Calculating Energy Required to change Temperature
An Erlenmeyer flask contains 52.0 g of water. Assuming there are no heat
losses, calculate the energy required to raise the temperature of the assembly
from 25.0 oC to 40.0 oC. (hint: Calculate the energy required for the flask and
water separately and then add the result.)
Data: Flask heat capacity = 175 J oC-1; specific heat (water) = 4.184 Jg-1 oC-1
Solution:
a) Calculate the temperature change:
∆T = Tfinal - Tinitial
= (40.0 – 25.0) oC = 15.0 oC
b) Calculate the energy required to heat the flask
q flask = C × ∆T
= 175 JoC-1 × 15.0 oC = 2625 J
c) Calculate the energy required to heat the water:
q water = m × S × ∆T
= 52.0 g × 4.184 Jg-1 oC-1 × 15.0 oC = 3264 J 213
The total energy required to heat the entire assemble is:
q = q flask + q water = 2625 J + 3264 J = 5889 J = 5.9 KJ
Suppose that the flask and its contents were now allowed to cool
from 40.0 oC to 25.0 oC. How much energy is lost by the flask
and water as they cool down? Logic dictates that it must also be
5.9 kJ. How do we differential between energy lost and energy
gained?
The convention used is when a system (the collection of
chemical and apparatus) gains energy, the process is
endothermic and the change in energy is positive. Conversely,
when the system loses energy, the process is exothermic and
the change in energy is negative. For the example above, the
change in energy for the system (flask plus water) q, is +5.9 kJ
as heats up, and – 5.9 as it cools down.
q is + when the heat flows into the system from the surroundings
q is – when heat flows out of the system into the surroundings

214
 Energy Changes in Chemical Reactions
Heat is the transfer of thermal energy between two bodies that
are at different temperatures.

Temperature is a measure of the thermal energy.

Temperature = Thermal Energy

900C 400C
greater thermal energy
215
 Example:
A 466 g sample of water is heated from 8.50 oC to 74.60
oC. Calculate the amount of heat absorbed by the water.

Reasoning and Solution: Using the mass and specific

heat of water and the temperature change in Equation,
we calculate the heat change as follows:
∆T = 74.60 oC – 8.50 oC = 66.1 oC
Specific Heat of water =4.184J/g oC
q = m × S × ∆T
q = (466 g × 4.184 Jg-1 oC-1)×(74.60 oC – 78.50 oC) = 1.29× 105 J
= 129 kJ

216
Measuring Heat: Calorimetry
Calorimetry is an experimental technique in which a colorimeter is used to study the
thermodynamics of chemical and physical processes.
Constant-Volume Calorimetry
FIGURE 6.6 A constant-volume bomb
calorimeter. The calorimeter is filled with oxygen
gas before it is placed in the bucket. The sample
is ignited electrically, and the heat produced by
the reaction can be accurately determined by
measuring the temperature increase in the known
amount of surrounding water.
qsys = qwater + qbomb + qrxn= 0

q = msΔt
qwater = (mwater)(4.184 J/g . oC)Dt
Cbomb = mbomb × Sbomb
Reaction at Constant V qbomb = CbombDt
ΔH = qrxn ΔH ~ qrxn
Where qwate , qbomb ,and qrxn are the heat change for the water, the bomb, and the reaction
, respectively. Thus
217
Example:
A quantity of 1.435 g of naphthalene (C10H8) , was burned in Constant-Volume
bomb Calorimeter. Consequently the temperature of the water rose from 20.17 oC to
25.84 oC, if the mass of water surrounding the calorimeter was exactly 2000 g and
the heat capacity of the bomb calorimeter was 1.80 kJ/oC, calculate the heat of
combustion of naphthalene on a molar basis; that is, find the molar heat of
combustion.
Reasoning and Solution: because this is isolated system, the heat generated
from the combustion must be equal to the heat gained by the water and colorimeter
using Equation. q = ms∆t

qwater = (2000 g)(4.184 J/g.oC)(25.84 oC – 20.17 oC) = 4.74 × 104 J

qbomb = Cbomb∆t= (1.80 × 103 J/oC )(25.84 oC – 20.17 oC) = 1.02 ×104 J
qrxn = - (qwater + qbomb) = - (4.74 × 104 J + 1.02 × 104 J) = -5.76 × 104 J
The molar mass of naphthalene is 128.2g, so the heat of combustion of
1 mole of naphthalene is 4 - 5.76  10 J 128 g C10 H 8
molar heat of combustion    - 5.15  10 6 J/mol  - 5.15  10 3 kJ mol
1.435 g C H 1 mol C H
10 8 10 8

218
Preactic Exercise:

A quantity of 1.922 g of methanol (CH3OH) , was

burned in Constant-Volume bomb Calorimeter.
Consequently the temperature of the water rose by
4.20 oC, if the quantity of water surrounding the
calorimeter was exactly 2000 g and the heat capacity of
the calorimeter was 2.02 kJ/oC, calculate the molar heat
of combustion of methanol.

219
 Constant-Pressure Calorimetry
Or Coffee-cup calorimeter

qsys = qwater + qcal + qrxn

qsys = 0
Figure 6.7 qrxn = - (qwater + qcal)
A constant-pressure calorimeter mad
qwater = msΔt
of two Styrofoam coffee cups. The
outer cup helps to insulate the qcal = CcalΔt
reacting mixture from the
surroundings. Two solutions of Reaction at Constant P
known volume containing the ΔH = qrxn
reactants at the same temperature
are carefully mixed in the calorimeter.
The heat produced or absorbed by
the reaction can be determined by 6.4
220
measuring the temperature change
 Constant-pressure Calorimetry
Example:
A quantity of 1.00 × 102 ml of 0.500 M HCl is mixed with 1.00 × 102 ml of 0.500 M
NaOH in constant-pressure Calorimeter that has a heat capacity of 335 J/oC. The
initial temperature of the HCl and NaOH solution is the same , 22.50 oC and the
final temperature of mixed solution is 24.90 oC. Calculate the heat change for the
neutralization reaction
NaOH (aq) + HCl (aq) NaCl (aq) + H2O (l)
Assume that the densities and specific heat of the solutions are the same as for
water (1.00 g/mL and 4.184 J/g. oC, respectively).
Reasoning and Solution: because the calorimeter is well insulated, we assume
that no heat is lost to the surroundings. Therefore, we can write
qsys = qsoln + qcal + qrxn
=0

qrxn = - (qsoln + qcal)

Or

221
 Constant-pressure Calorimetry
Because the density of the solution is 1.00 g/mL, the mass of 100-mL solution is
100g.
Thus
qsoln = (1.00 × 102 g + 1.00 × 102 g)(4.184 J/g.oC)(24.90 oC – 22.50 oC)
= 2.01 × 103 J

qcal = CcalΔt = (335 J/oC )(24.90 oC – 22.50 oC)

= 804 J
Next we write
qrxn = - (qsol + qcal) = - (2.01 × 103 J + 804 J) = -2.81 × 103 J = 2.81 kJ

For the molarities given, we know there is 0.0500 mole of HCl in 1.00 × 102 g of the
HCl solution and 0.0500 mol of NaHO in 1.00 × 102 g of the NaOH solution. Therefore the
heat of neutralization when -2.81
1.00 mol
kJ of HCl reacts with 1.00 mole of NaHO is

Heat of neutralization = 0.0500 mol = - 56.2 kJ/mol

comment: Because the reaction takes place at constant pressure, the heat given off
is equal to the enthalpy change. 222
 6.4
223
 Constant-pressure Calorimetry
Practice Exercise:
A quantity of 4.00 × 102 ml of 0.600 M HNO3 is mixed with 4.00 × 102 ml of 0.300 M Ba(OH)2 in constant-
pressure Calorimeter having a heat capacity of 387 J/oC. The initial temperature of both solutions is the
same at 18.88 oC. What is the final temperature of the solution? (Use the result in Example before for your
calculation.

224
Standard Enthalpy of Formation and reaction
So far we learn that we can determine the enthalpy change that accompanies a
reaction by measuring the heat absorbed or released (at constant pressure). From
Equation
(∆H = H (products) – H (reactants)) we see that ∆H can also be calculated if we know the
actual enthalpies of all reactants and products. Because there is no way to measure
the absolute value of the enthalpy of a substance, must I measure the enthalpy
change for every reaction of interest?
H o
The “sea level” freference point for all enthalpy expressions is called the standard
enthalpy of formation ( ), which is defined as the heat change that results
when one mole of a compound is formed from its elements at a pressure of 1 atm.
Elements are said to be in the standard state at 1 atm, hence the tern “standard
enthalpy “ . The superscript “o” represent standard-state conditions (1 atm), and the
subscript “f” stands for formation. Although the standard state does not specify a
temperature , we will allays use value measured at 25 oC.

The table 6.3 lists the standard enthalpies of formation for a number of elements and
compounds.

225
 6.5
226
Standard Enthalpy of Formation and reaction
By convention , the standard enthalpy of formation of any element in its most
stable form is zero. Take oxygen as an example. Molecular oxygen (O2) is
more stable than the other allotropic form of oxygen , (O3), at 1 atm and 25 oC.
Thus we can write
ΔH o (O )  0 ΔH o (C, graphite)  0
f 2 f
but
ΔH o (O )  0 ΔH o (C, diamond)  0
f 3 f

ΔH o (O )  0 ΔH o (C, graphite)  0
f 2 f
ΔH o (O )  142 kJ/mol ΔH o (C, diamond)  1.90 kJ/mol
f 3 f

6.5
227
The importance of the standard enthalpies of formation is that once we know their
H rxn
value, we can calculate the standard enthalpy oof reaction defined as the
enthalpy of a reaction carried out at 1 atm.
For example, consider the hypothetical reaction

aA  bB  cC  dD
Where a, b, c , and d are stoichiometric coefficients. For this reaction H rxn
o
is given
by
ΔH 0  [ c H 0 (C)  d ΔH 0 (D)]  [a ΔH 0 (A)  b ΔH 0 (B)]
rxn f f f f

Where a, b, c, and d are the moles. We can generalize the above equation
ΔH 0
 Σ n ΔH (products)
0
 0
Σ m ΔH (reactants)
rxn f f

When m and n denote the stoichiometric coefficients (in moles) for the reactants and
products, and ∑ (sigma) means “the sum of”.

228
In order to use Equation

H 0  [ c H 0 (C)  d H 0 (D)]  [a H 0 (A)  b H 0 (B)]

rxn f f f f

to calculate H rxn
o H of
we must know the values of the compounds that
take part in the reaction. To determine these values we can apply the direct
method or the indirect method.
The Direct Method. This method of measuring H of works for compounds that
can be readily synthesized from their elements. . Suppose we want to know the
enthalpy of formation of carbon dioxide. We must measure the enthalpy of the
reaction when carbon (graphite) and molecular oxygen in their standard states are
converted to carbon dioxide in its standard state:
o
C (graphite)  O (g)  CO (g) H  - 393.5 kJ
2 2 rxn

As we know from experience, this combustion easily goes to completion. From Equation
above we can write
0 0 0 0
H  ( 1 mol) H (CO .g)  (1 mol) H (C, graphite)  (1 mol) H (O .g)]  -393.5 kJ
rxn f 2 f f 2

229
Because both graphite and O2 are stable allotropic from, it follows 0
Hthat
(C, graphite)
f
0
and H f (O 2 .g) are zero. Therefore
0 0
ΔH rxn  ( 1 mol) ΔH f (CO 2 .g)  -393.5 kJ
0
H f (CO 2 .g)  -393.5 kJ

Other compounds that can be studied by the direct method are SF6, P4O10, and
CS2. The equations representing their syntheses are
S (rthombic)  3F2 (g)  SF6 (g)

P4 (white)  5O 2 (g)  P4 O 10 (s)

C (graphite)  2S (rhombic)  CS 2 (l)

Note that S(rhombic) and P(white) are the

H o most stable allotropes of sulfur and
f o
phosphorus, respectively, at 1 atm and 25 C, so their values are zero.

230
 Benzene (C6H6) burns in air to produce carbon dioxide and liquid water. How much heat is
released per mole of benzene combusted? The standard enthalpy of formation of benzene is
49.04 kJ/mol and standard enthalpy of formation of CO2 is – 393.5 kJ/mol

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

H0rxn = S nH0 f(products) - S mH0f (reactants)

H0rxn = 6H0f (H2O ) ] - [ 2H0 (C6H6)

[ 12H0 (CO2) + ]
f f

H0rxn = [ 12x–393.5 + 6x–187.6 ] – [ 2x49.04 ] = -5946 kJ

-5946 kJ
= - 2973 kJ/mol C6H6
2 mol

6.5
231
 The indirect Method . Many
compounds cannot be directly synthesized from their
elements. In some cases, the reaction proceeds too slowly , or side reaction
produce substances other than the desired compound.H
o
In fthese cases can
be determined by an indirect approach, which is based on the law of heat
summation (or simply Hass’s law).
Hess’s Law: When reactants are converted to products, the change in enthalpy is the same whether
the reaction takes place in one step or in a series of steps.

In otherwords,
o
H if we can break down the reaction
ofH o
interest into a series of
rxn rxn calculate
reaction for which can be measured. We can for the
overall react

(Enthalpy is a state function. It doesn’t matter how you get there, only where you start and
end.)

232
Let’s say we are interested in the standard enthalpy of formation of methane (CH4). We might
represent the synthesis of (CH4) from its elements as
C ( graphite )  2H 2 (g)  CH 4 (g)
However , this reaction does not take place as written , so we cannot measure the enthalpy
change directly. We must employ an indirect route, based on Hess’s law. To begin with, the
following reaction involving C, H2, and CH4 with O2 have all been studies and the
values are accurately known H
o

rxn

o
(a) C(graphite)  O 2 (g)  CO 2 (g) ΔH rxn  393.5kJ
o
(b) 2H 2 (g)  O 2 (g)  2H 2 O(l) ΔH rxn  571.65kJ
o
(c) CH 4 (g)  2O 2 (g)  CO 2 (g)  2H 2 O(l) ΔH rxn  890.4kJ

233
Since we want to obtain one equation containing only C and H2 as reactants and CH4 as
product , we must reverse ( c ) to get

o
(d) CO2 (g)  2H 2 O (l)  CH 4 (g)  2O 2 (g) ΔH  890.4kJ
rxn

The next step is to add Equations (a), (b), and (d)

o
(a) C(graphite)  O 2 (g)  CO 2 (g) ΔH rxn  393.5kJ
o
(b) 2H 2 (g)  O 2 (g)  2H 2 O(l) ΔH rxn  571.65kJ
o
(c) CO 2 (g)  2H 2 O(l)  CH 4 (g)  2O 2 (g) ΔH rxn  890.4kJ

o
(e) C(graphite)  2H 2 (g)  CH 4 (g) ΔH rxn  74.7kJ

234
The general rule in applying Hess’s law is that :
we should arrange a series of chemical equations (corresponding to a series of steps) in
such a way that.
When added together , all species will cancel except for the reactants and products that
appear in the overall reaction. This means that we want the elements on the left and the
compound of interest on the right of the arrow.
To achieve this , we often need to multiply some or all of the equations representing the
individual steps by the appropriate coefficients. The following example shows this approach .

235
Example:
Calculate the standard enthalpy of formation of acetylene (C2H2) from its elements:

The equations fro each step and the corresponding enthalpy changes are:

2C(graphite)  H 2 (g)  C 2 H 4 (g)

o
(a) C(graphite)  O 2 (g)  CO 2 (g) ΔH rxn  393.5kJ
o
(b) H 2 (g)  1/2O 2 (g)  H 2 O(l) ΔH rxn  285.8kJ
o
(c) 2C 2 H 2 (g)  5O 2 (g)  4CO 2 (g)  2H 2 O(l) ΔH rxn  2598.8kJ

Reasoning and Solution: Because we want to obtain one equation containing the element C. and
H2 as reactants and C2H4 as product, which represents the synthesis of acetylene from its
elements, we need to eliminate O2, CO2, and H2O from Equations (a), (b) , and (c) . We note
that (c) contains 5 moles of O2, 4 moles of CO2, and 2 moles of H2O. First we reverse ( c) to
get C2H2 on the product side:

o
(d) 4CO2 (g)  2H 2 O(l)  2C 2 H 2 (g)  5O 2 (g) ΔH rxn  2598.8kJ

236
Next , we multiply (a) by 4 and (b) by 2 and carry out the addition of 4 (a) + 2(b) + (d):

o
4C(graphite)  4O 2 (g)  4CO 2 (g) ΔH  4  393.5kJ
rxn
o
 2H 2 (g)  O 2 (g)  2H 2 O(l) ΔH rxn  2  285.8kJ
o
 4CO (g)  2H O(l)  2C H (g)  5O (g) ΔH rxn   2598.8 kJ
2 2 2 2 2
o
4C(graphite)  2H 2 (g)  2C 2 H 2 (g) ΔH rxn  453.2kJ
o
2C(graphite)  H 2 (g)  C 2 H 2 (g) ΔH rxn  226.6kJ
Or
Because the above equation represent the synthesis of C2H2 from its elements, we have
. (when the equation is divided by 2, the value ΔH
of rxn is halved.)

0
ΔH f (C 2 H 2 )  ΔH rxn / mol   226.6 kJ/mol

237
 Calculate the standard enthalpy of formation of CS2 (l) given that:

C(graphite) + O2 (g) CO2 (g) H0 =rxn-393.5 kJ

S(rhombic) + O2 (g) SO2 (g) H0 =
rxn-296.1 kJ
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) H0 = -1072 kJ
rxn
1. Write the enthalpy of formation reaction for CS2

C(graphite) + 2S(rhombic) CS2 (l)

2. Add the given rxns so that the result is the desired rxn.

C(graphite) + O2 (g) CO2 (g) H0rxn = -393.5 kJ

2S(rhombic) + 2O2 (g) 2SO2 (g) Hrxn
0 = -296.1x2 kJ

+ CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) H0rxn = +1072 kJ

C(graphite) + 2S(rhombic) CS2 (l)

H0rxn = -393.5 + (2x-296.1) + 1072 = 86.3 kJ

238
Practice Exercise:
Calculate the standard enthalpy of formation of carbon disulfide (CS2) from its elements , given
that

o
(a) C(graphite)  O 2 (g)  CO 2 (g) ΔH  393.5kJ
rxn
o
(b) S(rhombic)  O 2 (g)  SO 2 (g) ΔH  296.1kJ
rxn
o
(c) CS 2 (l)  3O 2 (g)  CO 2 (g)  2SO 2 (g) ΔH  1072kJ
rxn

239
We can calculate the enthalpy of reaction form values 0
H of
f
as shown in the
following example.
Example:
Pentaborane-9 , B5H9, is a colorless, highly reactive liquid that will burst into flame
or even explode when exposed to oxygen. The reaction is
2B5 H 9 (l)  12O 2 (g)  5B 2 O 3 (s)  9H 2 O (l)

Pentaborane-9 was considered as potential rocket fuel in the 1950s because it

produces a large amount of heat per gram. However , the sold B2O3 formed by
the combustion of B5H9 is an abrasive that would quickly destroy the nozzle of
the rocket , and so the idea was abandoned. Calculate the kilojoules of heat
released per gram of the compound reacted with oxygen . The standard enthalpy
of formation of B5H9 is 73.2 kJ/mol, B2O3(s) is -1263.6 kJ/mol, H2O (l) is -285.8
kJ/mol , and O2 (g) is0 kJ/mol
Reasoning and Solution: To calculate the standard enthalpy of reaction , we
look up the values of the reactants and products in Appendix 3 and use the
coefficients in the balanced equation

240
 H rxn
0
 [ c H 0f (C)  d H 0f (D)]  [a H 0f (A)  b H 0f (B)]
0 0 0 o 0
H rxn  [ (5 mol) H f (B 2 O 3 )  (9 mol) H f (H 2 O)]  [(2 mol) H f (B5 H 9 )  (12 mol) H f (O 2 )]

0
H rxn  [ (5 mol) ( -1263.6 kJ/mol)  (9 mol) ( -285.8 kJ/mol) ] 

[(2 mol) ( -73.2 kJ/mol)  (12 mol) ( o kJ/mol) ]  - 9036.6 kJ

This is the amount of heat released for every 2 moles of B2H9 reacted. The heat
released per gram of B5H9 reacted is

1mol B5 H 9  9036.69 kJ
heat released per gram of B 5 H 9  
63.12 g B5 H 9 2 mol B5 H 9

 - 71.58 kJ/g B 5 H 9

241
Practic Exercise:

Benzene (C6H6) burns in the air to produce carbon dioxide and liquid water.
Calculate the heat released (in kilojoules) per gram of the compound reacted
with oxygen. The standard enthalpy of formation of benzene is 49.04 kJ/mol.

242
Heat of Solution and Dilution
Although we have focused so far on thermal energy effects resulting from
chemical reaction , many physical processes, such as the melting of ice or the
condensation of a vapor, also involve the absorption or release of heat. Enthalpy
changes occur as well when a solute dissolves in a solvent or when a solution is
diluted. Let us look at these two related physical processes, involving heat of
solution and heat of dilution.
Heat of Solution
In the vast majority of case , dissolving a solute in solvent produces measurable
heat change. At constant pressure , the heat change is equal to the enthalpy
change.
The heat of solution , or enthalpy of solution , H soln , is the heat generated or
absorbed when a certain amount of solute dissolves in certain amount of solvent.
The quantity H soln represent the difference between the enthalpy of final
solution and the enthalpy of its original component (that is, solute and solvent)
before they are mixed. Thus

H soln  H soln - H components

243
The enthalpy of solution (Hsoln) is the heat generated or absorbed
when a certain amount of solute dissolves in a certain amount of solvent.

Hsoln = Hsoln - Hcomponents

Which substance(s) could be

used for melting ice?

Which substance(s) could be

used for a cold pack?

6.6
244
Neither H soln nor H components can be measured, but their difference,
H soln , can be readily determined in a constant-pressure calorimeter. Like other
enthalpy changes , H soln is positive for endothermic (heat-absorbing) processes and
negative for exothermic (heat-generating) processes.

Consider the heat of solution of a process in which an ionic compound is the solute
and water is the solvent. For example , what happens when solid NaCl dissolves in
water? In solid NaCl, the Na + and Cl – ions are held together by strong positive-
negative (electrostatic) forces, but when a small crystal of NaCl dissolves in water ,
the three-dimensional network of ions breaks into its individual units. (The structure
of solid NaCl is shown in figure 2.13)

245
 The Solution Process for NaCl
Figure 2.13

ΔHsoln = Step 1 + Step 2 = 788 – 784 = 4 kJ/mol

6.6
246
The separated Na+ and Cl- ions are stabilized in solution by their interaction with
water molecules. These ions are said to be hydrated . In this case the water plays a
role similar to that a good electrical insulator. Water molecules shield the ions (Na+
and Cl-) from each other and effectively reduce the electrostatic attraction that held
them together in the solid state. The heat of solution is defined by the following
process:

Na Cl (s)  Na
H 2O -
(aq)  Cl (aq) ΔH soln  ?

We can imaging that the solution process takes place in two separate steps:
First : the Na + and Cl- ions in the solid crystal are separated from each other and
converted to the gaseous state

Energy  Na Cl (s)  Na -
(g)  Cl (g)

The energy required to completely separate one mole of a solid ionic compound into
gaseous ions is called lattice energy (U). The lattice energy of NaCl is 788 kJ/mol.
In other words, we would need to supply 788 kJ of energy to break 1 mole of solid
NaCl into 1 mole of Na+ ions and 1 mole of Cl- ions.

247
Next , the “gaseous” Na+ and Cl- ions enter the water and become hydrated:

 
Na (g )  Cl (g)
-
 Na
H 2O -
(aq)  Cl (aq)  energy

The enthalpy change associated with the hydration process is called the heat of
hydration , H hydr ( heat of hydration is a negative quantity for cations and
anions). A applying Hess’s law, it is possible to consider as the sum of two
related quantities, lattice energy (U) and heat of hydration :
 
NaCl (s)  Na (g)  Cl (g)
-
U  788kJ

H O
Na  (g)  Cl - (g) 2
  Na  (aq)  Cl - (aq) H  784 kJ
hydr

NaCl (s) H

2O
 Na  (aq)  Cl - (aq) H hydr  4 kJ

Therefore , when 1 mole of NaCl dissolves in water , 4 kJ of heat will be absorbed

from the surrounding s. We would observe this effect by noting that the beaker
containing

248
the solution becomes slightly colder. The table 6.4 lists the H soln of several ionic
compounds . Depending on the nature of the cation and anion involved , H soln for
an ionic compound many be either negative (exothermic) or positive (endothermic).

249
Heat of Dilution
When a previously prepared solution is diluted, that is, when more solvent added to
lower the overall concentration of the solute, additional heat is usually given off or
absorbed. The heat of dilution is the heat change associated with the dilution
process. If a certain solution process is endothermic and the solution is
subsequently diluted, more heat will be absorbed by the same solution from the
surroundings, the converse holds true for an exothermic solution process __ more
heat will be liberated if additional solvent is added to dilute the solution. Therefore,
always be cautious when working on a dilution procedure in the laboratory.
Because of its highly exothermic heat of dilution, concentrated sulfuric acid (H2SO4)
poses a particularly hazardous problem if its concentration must be reduced by
mixing it with additional water. Concentrated H2SO4 is composed of 98 percent
acid and 2 percent water by mass. Diluting it with water releases considerable heat
to the surroundings. This process is so exothermic that you must never attempt to
dilute the concentrated acid by adding water to it. The heat generated could cause
the acid solution to boil and splatter. The recommended procedure is to add the
concentrated acid lowly to the water (while constantly stirring)

250
 Introduction to thermodynamics
Thermodynamic is p\rt of a broader subject called thermodynamics , which is
the scientific study of the interconversion of heat and other kinds of energy.
The laws of thermodynamics provide useful guidelines for understanding the
energetic and directions of processes. In this section we will concentrate on
the first law of thermodynamics.
In thermodynamics, we study changes in the state of a system, which is
defined by the values of all relevant macroscopic properties, for
example, composition, energy, temperature, pressure, and volume.
energy, pressure, volume, and temperature are said to be state function
__properties that are determined by the state of the system , regardless of
how that condition was achieved. In other words, when the state of a system
change, the magnitude of change in any state function depends only on the
initial and final states of the system and not on how the change is
accomplished
State functions are properties that are determined by the state of the system, regardless of how that
condition was achieved.

251
The state of a given amount of a gas is specified by its volume,
pressure, and temperature. Consider a gas at 2 atm, 300 K, and 1 L (the
initial state). Suppose a process is carried out at constant temperature
such that the gas pressure decrease to 1 atm. According to Boyle’s law,
its volume must be increase to 2 L. the final state then corresponds to 1
atm, 300 K, and 2L. The change in volume (∆V) is

V  V f - Vi

 2L - 1L  1L

252
When Vi and Vf denote the initial and final volume , respectively. No matter how
we arrive at the final state (for example, the pressure of the gas can be increased
first and then decreased to 1 atm), the change in volume is always 1 L. Thus the
volume of a gas is a state function. In a similar manner we could show that
pressure and temperature are also state functions.
Energy is another state function. Using potential energy as an example, we find
that the net increase in gravitational potential energy when we go from the same
staring point to the top of a mountain is always the same, regardless of how we
get there
(figure 6.9)
Potential energy of hiker 1 and hiker 2 is
the same even though they took
different paths.

253
 The first law of Thermodynamics

The first law of Thermodynamics , which basrd on the law of conservation of

energy, states that energy can be converted from one form to another, but
cannot be created or destroyed.
we can test the validity of the first law by measuring only the change in the
internal energy of the system between its initial state and final state. The change
in internal energy ∆E is given by

 E  E f - Ei
Where Ei and Ef are the internal energies of the system in the initial and final
states, respectively.

254
 Thermodynamics
∆E = q + w

∆E is the change in internal energy of a system

q is the heat exchange between the system and the surroundings

w is the work done on (or by) the system

w = -P∆V when a gas expands against a constant external pressure

255
 Enthalpy and the First Law of Thermodynamics
E = q + w
At constant pressure, q = H and w = -PV
E = H - PV
H = E + PV

256
Chemical Kinetics

257
 Chemical Kinetics
• In learning chemical kinetics, you will learn
how to:
– Predict whether or not a reaction will take place.
– Once started, determine how fast a reaction will
proceed.
– Learn how far a reaction will go before it stops.

258
 Rate of a Reaction
• Thermodynamics- Does a reaction take place?
• Kinetics- How fast does a reaction proceed?
• Chemical Kinetics- the area of chemistry concerned
with the speeds or rates at which a chemical reaction
occurs.
• Reaction Rate- the change in the concentration of a
reactant or product with time. (M/s)

259
 Rate of a Reaction
• Why do we need to know the rate of a
reaction?
– Practical knowledge is always useful
– Preparation of drugs
– Food processing
– Home repair

260
 Rate of a Reaction
• Chemical kinetics is the area of chemistry concerned
with the speeds, or rates, at which a chemical
reaction occurs.
• The word “kinetic” suggests movement or change; in
chapter 5 (Gases) we defined kinetic energy as the
energy available because of the motion of an object.
• Here kinetics refers to the rate of a reaction, Or the
reaction rate, which is the change in the
concentration of a reactant or a product with time
(M/s).

261
 Rate of a Reaction
• General equation for a reaction:
– A→B
– Reactant → Product
• In order to monitor a reaction’s speed or rate, we can
look at one of two things:
– Decrease in [ reactant ]
– Increase in [ product ]
– Can be represented as:
rate = - Δ [A] / Δ t or
rate = Δ [B] / Δ t
Where Δ [A] and Δ [B] are the change in concentration
(molarity) over a time period Δt.

262
Rate of a Reaction

263
 Rate of a Reaction

The rate of reaction A B,

represented as the decrease of A
molecules with time and as the
increase of B molecules with time

264
 Rate of a Reaction
• How do we measure this experimentally?
– For reactions in solution:
• Changes in concentration can be measured
spectroscopically
– For reactions involving gases:
• Changes in pressure can be measured
– For reactions in solution with ions present:
• Change in concentrations can be measured through
electrical conductance

265
 Rate of a Reaction
Reaction of Molecular Bromine and Formic Acid
• So if we have an aqueous solution of molecular bromine
and formic acid (HCOOH), how do we determine the
reaction rate?
• Br2(aq)+HCOOH(aq) → 2Br–(aq)+2H+(aq)+CO2 (g)

time

From left : the decrease in bromine concentration as time

elapses shows up as loss of color. 266
 Rate of a Reaction

• Look for color changes

• Molecular bromine is usually reddish-brown in
color. Formic acid is colorless.
• As the reaction progresses, the color of the
solution changes.
• It fades until it becomes colorless.
• What does this mean?

267
 Rate of a Reaction
Plot of absorption of bromine
versus wavelength. The
maximum absorption of visible
light by bromine occurs at 393
nm. As the reaction
progresses, the absorption,
which is proportional to [Br2],
decreases with time, indicating
a depletion in bromine.

268
 Rate Calculations
• How do we calculate the rate of a reaction?
– We first need this information:
• Time (s)
• [reactant]

269
 Rate Calculations
Br2 (aq) + HCOOH (aq) → 2Br– (aq) + 2H+ (aq) + CO2 (g)

270
 Rate Calculations

• Instantaneous Rate– rate of a reaction for a

specific point in time.
• Average Rate vs. Instantaneous rate
– Examples????

271
 Rate Calculations
• Average Rate =
-Δ [Br2] / Δt = - [Br2]final – [Br2]initial / [t]final – [t]initial

• Instantaneous Rate =

rate for specific instance in time

[Br2] / t

272
 Rate Calculations
• Using this information,
calculate the average rate of the
bromine reaction over the first
50s of the reaction.

273
Table13.1
Rates of the reaction between molecular bromine and formic acid at 25 oC

Time (s) [Br2] rate (M/s) k = rate/[Br2](s-1)

0.0 0.012 4.20 x 10-5 3.50 x 10-3

50.0 0.010 3.52 x 10-5 3.49 x 10-3
100.0 0.008 2.96 x 10-5 3.50 x 10-3
150.0 0.007 2.49 x 10-5 3.51 x 10-3
200.0 0.006 2.09 x 10-5 3.51 x 10-3
250.0 0.005 1.75 x 10-5 3.50 x 10-3
300.0 0.004 1.48 x 10-5 3.52 x 10-3
350.0 0.0035 1.23 x 10-5 3.48 x 10-3
400.0 0.003 1.04 x 10-5 3.51 x 10-3

274
 Rate Calculations

Average Rate = - [Br2]final – [Br2]initial / [t]final – [t]initial

Average Rate = - (0.0101- 0.0120)M / (50s – 0s)

Average Rate = -0.002M / 50s

Average Rate = 3.80 x 10-5 M/s

275
 Average Rate

The instantaneous
rates of the reaction
between molecular
bromine and formic
acid at t=100 s, 200
s, and 300 s are
given by the slopes
of the tangents at
these times
276
The rate of the bromine-formic acid reaction also depends on the
concentration of formic acid. However, by adding a large excess of
formic acid to the reaction mixture we can ensure that the
concentration of formic acid remains virtually constant throughout the
course of the reaction.
Under this condition the change in the amount of formic acid present
in solution hase no effect on the measured rate.

277
Let’s consider the effect that the bromine concentration has no the rate of
reaction. Look at the data in Table 13.1. compare the concentration of
Br2 and the reaction rate at t= 50 s and t = 250 s. At t = 50 s, the bromine
concentration is 0.0101 M and the rate of reaction is 3.52 x 10-5 M/s. at t
= 250 s, the bromine concentration is 0.00500 M and the rate of reaction
is 1.75 x 10-5 M/s. the concentration at t 50 s is double the concentration
at t = 250 s (0.0101 M versus 0.00500 M), and the rate of reaction at t =
50 s is double the rate at t = 250 s (3.52 x 10-5 M/s versus 1.75 x 10-5
M/s).
We see that as the concentration of bromine is double, the rat of reaction
also double. Thus, the rate is directly proportional to the Br2
concentration, that is
rate α [Br2 ]

rate  k [Br2 ]
-5
rate 3.52  10 M/s 3 1
k    3.49  10 s
[Br2 ] 0.0101 M

K is known a the rate constant, 278

Because reaction rate has the units M/s, and [Br2] is in M, the unit of
k is 1/s or s-1 in this case. It is important to understand that k is not
affected by the concentration of Br2

279
Reaction Rates and Stoichiometry
• For reactions more complex than A → B we
cannot use the rate expression initially
described.
• Example:
– 2A → B
– Disappearance of A is twice as fast formation of B
– Rate = - ½ Δ[A] /Δt

280
 Reaction Rates and Stoichiometry

• In general, for the reaction

– aA + bB → cC + dD

– Rate =
- 1/a Δ[A] /Δt = - 1/b Δ[B] /Δt = 1/c Δ[C] /Δt = 1/d Δ[D] /Δt

281
 Reaction Stoichiometry

Write the rate expression for the following reaction:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

Δ[CH4] 1 Δ[O2] Δ[CO2] 1 Δ[H2O]

rate = - =- = =
Δt 2 Δt Δt 2 Δt

282
283
284
285
 Rate Constant

• Look back to molecular bromine chart.

• What is k?
– K- the rate constant. A constant of proportionality between
the reaction rate and the concentration of the reactant.
– K may change slightly over time.
– K is represented as:
• K = rate/ [reactant]
• K is not affected by the [reactant] or rate alone, since it is a ratio of
these two. At any given point on a graph, k should be similar in
value to it’s value at other points in the same graph.

286
 The Rate Law

• Rate Law- expresses the relationship of the

rate of a reaction to the rate constant and the
concentrations of the reactants raised to some
power.
• Using the general reaction:
aA + bB → cC + dD
Rate Law is:
rate = k [A]x[B]y

287
 The Rate Law

aA + bB cC + dD

Rate = k [A]x[B]y

reaction is xth order in A

reaction is yth order in B
reaction is (x + y)th order overall

288
 Reaction Order

• Reaction Order- the sum of the powers to which all

reactant concentrations appearing in the rate law are
raised.
• Reaction order is always defined in terms of reactant
concentration.
• Overall reaction order- x + y
• Example:
• Rate = k [F2] [ClO2]
• Reaction order = first
• Overall reaction order = second

289
 Reaction Order

• What is the rate expression for

• aA + bB → cC + dD where x=1 and y=2?
– Rate = k[A][B]2
• What is the reaction order?
– First in A, second in B
• Overall reaction order?
– 2 +1 = 3

290
 Reaction Order

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2]x[ClO2]y
291
 Reaction Order
If initially [F2] = 1.0M and [ClO2]=1.0M, what will
happen to the reaction rate if F2 is doubled?

Rate1 = k(1.0M)(1.0M)2
Rate1 = k(1.0M3) [F2 ] = 1.0M

Rate2 = k(2.0M)(1.0M)2
Rate2 = k(2.0M3) [F2 ] = 2.0M

Rate2 = 2 x Rate1
292
 Reaction Order
What will happen in the same reaction if the
[ClO2] is doubled?

Rate1 = k(1.0M)(1.0M)2
Rate1 = k(1.0M3) [ClO2 ] = 1.0M

Rate2 = k(1.0M)(2.0M)2
Rate2 = k(4.0M3) [ClO2 ] = 2.0M

Rate2 = 4 x Rate1

293
Determination of Rate Law
F2 (g) + 2ClO2 (g) 2FClO2 (g)

Experiment [F2] [ClO2] Rate

(M/s)
1 0.04 0.03 1.0x10-2

2 0.04 0.04 2.0x10-2

3 0.02 0.04 1.0x10-2

4 0.04 0.06 2.0x10-2

294
 Determination of Rate Law
• Experiments 1 & 4
As [F2] doubles, so does the rate
• Experiments 2 & 3
As [ClO2] doubles, so does the rate
• 2:2 ratio…..1:1 ratio
x = 1 and y = 1
• Rate = k [F2] [ClO2]

295
 Rate law/Expression
Calculations
Determine the rate law and calculate the rate constant for the following
reaction from the following data:
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)

Initial Rate
Experiment [S2O82-] [I-] Double [I-], rate doubles (experiment 1 & 2)
(M/s)

1 0.08 0.034 2.2 x 10-4 Double [S2O82-], rate doubles (experiment 2 & 3)

rate = k [S2O82-]x[I-]y
2 0.08 0.017 1.1 x 10-4
y=1
3 0.16 0.017 2.2 x 10-4
x=1

rate = k [S2O82-][I-]

rate 2.2 x 10-4 M/s

k= = = 0.08/M•s
[S2O82-][I-] (0.08 M)(0.034 M) 296
 Rate Law/Reaction Order
Rate laws are always determined experimentally
Reaction order is always defined in terms of
reactant
Reactant order is not related to the stoichiomteric
coefficient in the overall reaction.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2][ClO2]

297
 Relation between Reactant
Concentration and Time
• First Order Reaction- a reaction whose rate
depends on the reactant concentration raised to
the first power.
Reaction Type: A→B
Rate of: -Δ [A]/Δt or k[A]
Combining and simplifying these equations
brings us to the following rate equation:
ln[A]t = -kt + ln[A0]

298
Relation between Reactant
Concentration and Time

299
 Reaction Time
The reaction 2A B is first order in A with a rate
constant of 2.8 x 10-2 s-1 at 800C. How long will it take for A
to decrease from 0.88 M to 0.14 M ?
ln[A] = ln[A]0 - kt [A]0 = 0.88 M
kt = ln[A]0 – ln[A] [A] = 0.14 M

[A]0 0.88 M
ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10-2 s-1
300
301
302
 Decomposition of Nitrogen
Pentoxide
• Data on page 560
• Plot of ln[N2O5] (M) vs. t (s) will allow us
to see and calculate more information
about the reaction taking place

303
Decomposition of Nitrogen
Pentoxide

304
 Gas Phase Reactions
• First order gas phase reactions have a
linear relationship between partial
pressure of gas and time.

lnPt = -kt + lnP0

305
306
307
Gas Phase Reactions

308
 Reaction Half-life
• As a reaction proceeds, the concentrations
of the reactants decreases.
• Another way to measure [reactant] over
time is to use the half-life.
• Half-life, t1/2 – the time required for the
concentration of a reactant to decrease to
half of its initial concentration.

309
 Reaction Half-life
• Expression for half-life of a first order
reaction is:

t1/2 = ln2/k
or
t1/2 = 0.693/k

310
Reaction Half-life

311
 Reaction Half-life
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?

t½ = ln2
k
0.693
t½ =
5.7 x 10-4 s-1

t½ = 1200 s

t½ = 20 minutes
312
313
 Second-Order Reactions
• Second-order reaction- a reaction whose rate depends
on the concentration of one reactant raised to the
second power OR on the concentrations of two different
reactants, each raised to the first power.

• Simple Type: A→B

– rate = k[A]2
• Complex Type: A + B→C
– rate = k[A][B]

314
 Second-order Reactions
• For A→B, the following expression is
used:
1 1
= + kt
[A] [A]0

315
 Half-life of a Second-order
Reaction
• Equation for half-life
1
t½ =
k[A]0

• What is the difference between this

equation and the equation for half-life of
first-order reactions?

316
317
318
 Zero-order Reactions
• Very rare reactions
• Usually occur on metallic surfaces
• Half-life Equation:
[A]0
t½ =
2k
• Reaction rate is described by:
– Rate = k
– Why?

319
Summary

320
Activation Energy and Temperature
Dependence of Rate Constants

321
 The Collision Theory of
Chemical Kinetics
• Gas molecules frequently collide with one
another
• Expect that the rate of a reaction is
equivalent to the number of collisions
• Reaction rate is dependent on
concentration

322
 The Collision Theory of
Chemical Kinetics
• Activation Energy (Ea)-
the minimum amount of
energy required to initiate
a chemical reaction.
• Activated Complex
(Transition State)- a
temporary species
formed by the reactant
molecules as a result of
the collision before they
form the product.

323
 The Collision Theory of
Chemical Kinetics
• What does this have to do with
temperature?
– High energy molecules
– High temperatures
– Increased product formation

324
 The Collision Theory of
Chemical Kinetics
• Factors that affect rate
– 1.
– 2.
– 3.

325
 The Arrhenius Equation
• Relation between activation energy and
temperature.

lnk = (Ea/R) x (1/T) + lnA

326
327
328
329
Rate Constants and
Temperature

lnK1 = Ea x (T1 – T2)

lnK2 R (T1T2)

330
331
Activation Energy, Reaction Rates
and Temperature
• As stated earlier, for a reaction to take
place, molecules must posses enough
kinetic energy.
• Kinetic energy must be higher than Ea.
• Each reaction takes place at a specific
temperature……but what happens if we
adjust this temp.?

332
Activation Energy, Reaction Rates
and Temperature
• Increasing Temperature leads to:
– Molecules reach high ke faster
– Number of molecules with high enough ke
increases
– Reaction rate increases

333
 Catalysts
• A catalyst is defined by the ability of a
substance to do each of the following:
– Catalysts increase the rate of reaction.
– Catalysts are not consumed by the reaction.
– A small quantity of catalyst should be able to
affect the rate of reaction for a large amount
of reactant.
– Catalysts do not change the equilibrium
constant for the reaction.

334
 Catalysts
• Heterogeneous catalyst- the reactants
and the catalyst are in different phases.
catalyst = solid reactants = liquid/gas
• Homogeneous catalyst- catalyst and
reactants are in the same phase, usually
liquid.

335
Catalysts

336
Enzyme Catalysts

337
Enzyme Catalysts

338
The End!!!!!!!

339