SOLUTION STOICHIOMETRY
Nature of Electrolytes
Reactions in aqueous solutions
Classes of Reactions in Aqueous Solutions
Common Terms Used In Titration
Oxidation-Reduction Reactions (Redox Reactions)
Balancing Oxidation-Reduction Reactions
Electrical conductivity
• When an Ionic compound dissociates to give adequately enough
ions to water, the solution will conduct electricity.
• Ionic compounds whose aqueous solutions conduct electricity are
called Electrolytes.
Types of Electrolytes:
• Strong electrolytes
They are "completely dissociated" into ions in aqueous solution.
H2SO4 (aq) 2H+ (aq) + 𝐒𝐎𝟐−
𝟒 (aq)
• Weak electrolytes
They are "Partially dissociated" into ions in aqueous solution.
An example of a weak electrolyte is acetic acid.
• CH3COOH(aq) → H+(aq) + CH3COO- (aq)
• Acetic acid solutions in water produce very few ions.
• You will even learn to calculate how many ions are produced.
Nonelectrolytes.
Do not conduct electricity in aqueous solution.
These compounds do not give any ions at all in water
solutions.
Examples:
Sugar, Ethylene glycol (antifreeze), Alcohol, etc.
Electrolyte Composition
•Dissolving an ionic substance gives equal positively and
negatively charged ions.
➢The total charge in the solutions is zero i.e resulting
solution is electrically neutral.
The positive ions are called Cations
•They are attracted to the cathode or the negative
electrode.
The negative ions are called Anions
•because they are attracted to the anode.
Reactions in aqueous solutions
Consider the reaction of HCl and NaOH in water:
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l).
• Except H2O, since HCl, NaOH and NaCl dissolved in
water to form ions:
we could - or should - write:
H+(aq) + Cl-(aq) + Na+(aq) + OH- (aq) → H2O(l) + Na+ (aq) + Cl- (aq)
Notice that the interesting part is:
H+(aq) + OH- (aq) → H2O(l)
• The Cl- (aq) and Na+(aq) occur on both sides of the equation.
• They can be canceled out.
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Spectator Ions
We call the Cl- (aq) and Na+ (aq) ions spectator ions.
• leave the spectator ions out when writing reactions in aqueous solution.
• The spectator ions have to be there in order to keep the solutions
electrically neutral,
• Their identity is not usually important to the chemistry taking place.
Another example:
Consider the Neutralization Reactions below:
• 2 HCl(aq) + Na2CO3(aq) → CO2(g) + H2O(l) + 2 NaCl(aq)
This is short for
2H+(aq) + 2Cl- (aq) + 2Na+(aq) +CO32- (aq) → CO2 (g) + H2O (l) + 2Na+(aq) + 2Cl- (aq)
When we strip out the spectator ions we get
✓ 2H+(aq) + CO32- (aq) → CO2(g) + H2O(l)
This is the interesting (or important) part of the reaction.
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The reaction that is left after we drop the spectator ions is
called the net ionic reaction or sometimes just the net
reaction.
• There must always be spectator ions in an ionic reaction,
but we don't always have to know what they are.
How do we know which ions to drop and which to keep?
Drop:
• aqueous ions that appear on both sides
Keep:
• Insoluble ionic compounds (like AgCl)
• Gases (like CO2)
• Water
• Nonionic compounds
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How do we know which ionic compounds are insoluble?
• There is a set of general solubility rules for ionic
compounds in water.
✓ Na+, K+, NH4+ compounds all soluble
✓ NO3- compounds all soluble
• Cl- , SO42- compounds soluble except AgCl, BaSO4,
PbSO4
• CO32- , PO43- , S2- , OH- , O2- compounds insoluble
except Ba(OH)2 (and, of course, compounds with Na+,
K+, and NH4+).
• Many times we can reason by analogy from these rules.
• For example AgCl is insoluble so we might expect that
AgBr and AgI would be insoluble too.
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Let's go back, now, and look at the examples we gave before:
H+(aq) + Cl- (aq) + Na+(aq) + OH- (aq)→ H2O(l) + Na+(aq) + Cl- (aq),
2H+(aq) + 2Cl-(aq)+2Na+(aq) +CO32-(aqC) → O2(g) +H2O(l) + 2Na+(aq) + 2Cl-(aq),
And another one we didn't see before:
AgNO3(aq) + NaBr(aq) → AgBr( ? ) + NaNO3(aq)
END OF SESSION
ONE
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Classes of Reactions in Aqueous Solutions
There are many possible chemical reactions.
Fortunately, we can find ways to classify reactions by
features they have in common.
One class of reactions is called exchange reactions.
Consider the reaction:
NaCl(aq) + KNO3(aq) KCl(aq) + NaNO3(aq).
Notice that the Ions have swapped partners.
That is what we mean by an exchange reaction.
However, this particular reaction has a problem.
If we write it in terms of aqueous ions we can see what
the problem is.
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Na+(aq) + Cl-(aq) + K+(aq) + NO3-(aq) Na+(aq) + NO3-(aq) + K+(aq) + Cl-(aq)
If we now look to strip out the spectator ions we see that all of the
ions are spectator ions.
So this reactions is not a reaction at all, it is just a mixture of ions.
The way to force a reaction to take place is to have one of the
compounds removed from solution.
This will happen if one of the products is an insoluble compound, or
water, or a gas.
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Precipitate formation:
BaCl2(aq) + Na2CO3(aq) BaCO3(s) + 2NaCl(aq)
If we recognize that everything in the reaction is a soluble ionic
compound, except the solid barium, and strip out the spectator
ions we get the net ionic reaction:
Ba2+(aq) + CO32- (aq) BaCO3(s)
When we mix aqueous barium chloride and aqueous sodium
carbonate we get a precipitate of barium carbonate.
The other ions are just along to maintain electrical neutrality.
Another example of a reaction forming a precipitate:
2AgNO3(aq) + K2S(aq) Ag2S(s) + 2KNO3(aq).
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Water formation
Acid-base reactions always form water (in the Arrhenius
picture of acids and bases).
The reaction is called Neutralization
For example:
HClO4(aq) + NaOH(aq) NaClO4(aq) + H2O(l).
Stripping out the spectator ions from this reaction leaves:
H+(aq) + OH- (aq) H2O(l),
which is the same for all acid base reactions.
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Quantitative Measurements in Acid Base Reaction-
TITRATION
Standard Solution
A solution containing a precisely known concentration of an
element or a substance.
Standardization
Is a process in which the concentration of the standard solution is
precisely established.
Titration-
An unknown amount of one reactant is combined exactly with a
precisely measured volume of a standard solution of the other.
End-point
When exactly stoichiometric amounts of two reactants have been
combined.
Indicator
Substance added to aid in detection of the endpoint (usually via a
color change)
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Vinegar is an aqueous solution of acetic acid, C2H3OOH.
A 12.5mL sample of vinegar was titrated with a 0.504 M
standard solution of NaOH. The titration required 15.40 mL of
the base solution (NaOH) in order to reach the endpoint.
What is the molar concentration of HC2H3O2 in vinegar?
Solution:
Step-1: Write and Balance the chemical reaction
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Step-4:
Consider Reaction Mole Ratio (eqn…i) from
Balanced reaction to get moles of Acetic Acid that
reacted!
Step-5:
Determine the Molar Concentration from eqn…(ii)
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Gas Formation
We have already seen some reactions which form CO2. For
example,
Na2CO3(aq) + H2SO4(aq) ®Na2SO4(aq) + CO2(g) + H2O(l).
Notice that the net ionic reaction is the same as our previous
reaction giving CO2
Let’s look at a different reaction.
Na2S(aq) + 2 HBr(aq) ® H2S(g) + 2 NaBr(aq).
What is the net ionic reaction?
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Oxidation-Reduction Reactions (Redox Reactions)
The concept of oxidation originally came from substances
reacting with oxygen.
• Matters reacting with oxygen were said to be oxidized.
• Example, iron will react with oxygen to give iron (III)
oxide.
4Fe(s) + 3O2(g) 2Fe2O3(s).
In the reaction, iron (Fe) is “oxidized”.
• Matters from which Oxygen is removed are said to be
reduced
Fe2O3(s) + 3 H2(g) 2 Fe(s) + H2O(l).
➢ the iron in the Fe2O3 has been "reduced."
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Observations
Oxygen is not always required to produce the same
change in the iron.
• The oxygen converted elemental iron, Fe into Fe3+ ions,
• This can be done in other ways without oxygen.
Example,
2Fe(s) + 3Cl2(g) 2FeCl3(s)
Chlorine, Cl also produces Fe3+ ions.
In order to define oxidation and reduction accurately we
must first define the terms Oxidation number or oxidation
state
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Oxidation number or oxidation state
✓ Is the hypothetical ionic charge on the element.
• If the element has formed a monatomic ion, then the oxidation
state is the ionic charge carried by the ion.
• An element may be incorporated into a molecule or molecular
ion and not really have an ionic charge of its own.
• Nevertheless, we look at the element as and ask what its ionic
charge would be if it were an ion.
Determining Oxidation Number
• An element in its elemental form has an oxidation number of
ZERO.
O2, N2, Fe, P4, S8, Cl2, etc. all have an oxidation number zero.
• Monatomic ions have an oxidation number equal to their
ionic charge.
• Cl- , O2- , Na+, Ca2+, Sn4+, H+, etc.
When an element is incorporated into a molecule or a molecular
ion we have to figure out its oxidation state from elemental matters
it is bonded to.
Oxygen in a compound is almost always - 2
hydrogen in a compound is almost always +1
Here are some examples which we will work out in class:
HNO3; SO42-; PO43-; Cr2O72-; B2O3.
Definations
Oxidation
Oxidation is an increase in oxidation number.
Oxidation always result in a loss of electrons.
Other tell-tale signs,
Gain of one or more O atoms
Loss of one or more H atoms
Reduction.
Reduction is a decrease in oxidation number.
Reduction always gives a gain of electrons.
Other tell-tale signs,
Loss of one or more O atoms.
Gain of one or more H atoms.
Balancing Redox Reactions
Balanced the following redox reactions:
SiO2 + 2 C Si + 2 CO
Identify what is being oxidized and what is being reduced in a
reaction.
Determine and note the oxidation numbers involved.
If something is oxidized something else has to be reduced.
If oxidation is a loss of electrons, the electrons don't just disappear.
Something else has to gain electrons.
The half-reaction method
Step 1
• Split the original equation into two half reactions, " one Reduction Half
reaction" and the other “Oxidation half Reaction
• In each reaction, follow these steps:
Step-2
• Balance all elements except “H” and “O”.
Step3
• Balance O by adding H2O to the appropriate side of each half reaction.
(Don't worry, if there isn't any water in the reaction the H2O's will cancel
out).
Step 4
• Balance H by adding H+ ions to the appropriate side. (Don't worry, if there
is no H+ in the reaction they will cancel out.)
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Step-5
• Balance the charge in each half reaction by adding electrons (e- ) as
needed.
Step-6
• Now add these two half reactions in such a way that the electrons cancel
out.
• That means that we may have to multiply one or both half reactions by a
small whole number to make the number of electrons on each side cancel.
Step-7
Recombine the two half reactions, cancel commons if needed.
• If you find that there are some H+'s left in the reaction then you have
balanced the reaction as if it were in an acid solution.
Step-8
• If you know that the reactions occurred in a basic solution then add
enough OH- ions to both sides of the balanced reactions so that the
H+ ions can all be converted to H2O.
• Here are some examples:
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Examples
Cr2O72- + Br- Cr2+ + Br2
Balance the following reaction in basic media
Cr(OH)3 + ClO3- CrO42- + Cl- ……..(Basic)
S2O32- + Cl2 Cl- + SO42-
CaC2O4(s) + MnO4-(aq) Mn2+(aq) + CO2 + Ca2+
SiO2 + 2 C Si + 2 CO
MnO4- + S2- MnO2 + SO42-
MnO4- + Fe2+ Mn2+ + Fe3+
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END
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