Reactions in Aqueous

11 Solutions II:
Calculations

1
Chapter Goals
Aqueous Acid-Base Reactions
1. Calculations Involving Molarity
2. Titrations
3. Calculations for Acid-Base Titrations
Oxidation-Reduction Reactions
4. Balancing Redox Equations
5. Adding in H+, OH- , or H2O to Balance Oxygen
or Hydrogen
6. Calculations for Redox Titrations

2
Calculations Involving Molarity
• Example 11-1: If 100.0 mL of 1.00 M
NaOH and 100.0 mL of 0.500 M H2SO4
solutions are mixed, what will the
concentration of the resulting solution be?
• What is the balanced reaction?
– It is very important that we always use a
balanced chemical reaction when doing
stoichiometric calculations.

3
Calculations Involving Molarity
2 NaOH + H 2SO 4  Na 2SO 4  2 H 2O
Reaction
Ratio: 2 mmol 1 mmol 1 mmol 2 mmol
Before
Reaction: 100
50 mmol 0 mmol 0 mmol
mmol
After
Reaction: 100
0 mmol 0 mmol 50 mmol
mmol
4
Calculations Involving Molarity

• What is the total volume of solution?

100.0 mL + 100.0 mL = 200.0 mL
• What is the sodium sulfate amount, in
mmol?
50.0 mmol
• What is the molarity of the solution?
M = 50 mmol/200 mL = 0.250 M Na2SO4
5
Calculations Involving Molarity
• Example 11-2: If 130.0 mL of 1.00 M KOH
and 100.0 mL of 0.500 M H2SO4 solutions
are mixed, what will be the concentration
of KOH and K2SO4 in the resulting
solution?
• What is the balanced reaction?

6
Calculations Involving Molarity
2 KOH + H 2SO 4  K 2SO 4 + 2 H 2 O
Reaction
Ratio: 2 mmol 1 mmol 1 mmol 2 mmol
Before
Reaction: 130 50 mmol 0 mmol 0 mmol
mmol
After
Reaction: 30 0 mmol 50 mmol 100
mmol mmol
7
Calculations Involving Molarity
• What is the total volume of solution?
130.0 mL + 100.0 mL = 230.0 mL
• What are the potassium hydroxide and
potassium sulfate amounts?
30.0 mmol & 50.0 mmol
• What is the molarity of the solution?
M = 30.0 mmol/230.0 mL = 0.130 M KOH
M = 50.0 mmol/230.0 mL = 0.217 M K2SO4
8
Calculations Involving Molarity
• Example 11-3: What volume of 0.750 M
NaOH solution would be required to
completely neutralize 100 mL of 0.250 M
H3PO4?
You do it!

9
Calculations Involving Molarity

3 NaOH + H 3PO 4  Na 3 PO 4 + 3 H 2 O
0.250 mol H 3 PO 4
? L NaOH = 0.100 L H 3PO 4  
1 L H 3PO 4
3 mol NaOH 1 L NaOH
  0.100 L NaOH
1 mol H 3 PO 4 0.750 mol NaOH

10
Titrations
Acid-base Titration Terminology
 Titration – A method of determining the concentration of
one solution by reacting it with a solution of known
concentration.
 Primary standard – A chemical compound which can be
used to accurately determine the concentration of another
solution. Examples include KHP and sodium carbonate.
 Standard solution – A solution whose concentration has
been determined using a primary standard.
 Standardization – The process in which the
concentration of a solution is determined by accurately
measuring the volume of the solution required to react with
a known amount of a primary standard.
11
Titrations
Acid-base Titration Terminology
 Indicator – A substance that exists in different forms
with different colors depending on the concentration of
the H+ in solution. Examples are phenolphthalein and
bromothymol blue.
 Equivalence point – The point at which
stoichiometrically equivalent amounts of the acid and
base have reacted.
 End point – The point at which the indicator changes
color and the titration is stopped.

12
Titrations
Acid-base Titration Terminology

13
Calculations for Acid-Base
Titrations
• Potassium hydrogen phthalate is a very
good primary standard.
– It is often given the acronym, KHP.
– KHP has a molar mass of 204.2 g/mol.


O A very common mistake is for students
O to see
CH C the acronym KHP and think CH that
C this
HC C OH Hpotassium,
C C -K +
Ohydrogen,
compound
+ KOH
is made of + H2O
HC C and
O phosphorous. HC C O
CH C CH C
OH OH acidic H
14
KHP
Calculations for Acid-Base
Titrations
• Example 11-4: Calculate the molarity of a
NaOH solution if 27.3 mL of it reacts with
0.4084 g of KHP.
NaOH + KHP  NaKP1 mol+ KHP
H 2O
? mol NaOH = 0.4084 g KHP  
1 mol KHP
204.2 g KHP
? mol NaOH = 0.4084 g KHP 
204.2 g KHP
1 mol NaOH
 0.00200 mol NaOH
1 mol NaOH
1 mol KHP  0.00200 mol NaOH
1 mol KHP
0.00200 mol NaOH
? M NaOH =  0.0733 M NaOH
0.0273 L NaOH

15
Calculations for Acid-Base
Titrations
• Example 11-5: Calculate the molarity of a
sulfuric acid solution if 23.2 mL of it reacts
with 0.212 g of Na2CO3.
Na 2 CO 3 + H 2SO 4  Na 2SO 4 + CO 2 + H 2 O
1 mol Na 2 CO3
? mol H 2SO 4 = 0.212 g Na 2 CO3  
You do it! 106 g Na 2CO3
1 mol H 2SO 4
 0.00200 mol H 2SO 4
1 mol Na 2 CO3
0.00200 mol H 2SO 4
? M H 2SO 4   0.0862 M H 2SO 4
0.0232 L H 2SO 4
16
Calculations for Acid-Base
Titrations
• Example 11-6: An impure sample of
potassium hydrogen phthalate, KHP, had a
mass of 0.884 g. It was dissolved in water
and titrated with 31.5 mL of 0.100 M NaOH
solution. Calculate the percent purity of the
KHP sample. Molar mass of KHP is 204.2
g/mol.
NaOH + KHP  NaKP + H2O
You do it!
17
Calculations for Acid-Base
Titrations
0.100
0.100 mmol
0.100
mmol mmol
NaOH NaOHNaOH
??mmol
mmol NaOH
? mmol
NaOH = =31.5
NaOH 31.5
= 31.5
mL mL solution
mL  
solution
solution
1 mL
1 mL mLsol'
1sol' n sol'n n
 3.315 3mmol
.15 .15 NaOH
mmol
mmol NaOH
NaOH
1 mmol KHP
? g KHP = 3.15 mmol NaOH  1 mmol KHP

? g KHP = 3.15 mmol NaOH  NaOH
mmol 
0.2042g KHP
mmol NaOH
0 . 2042 g  0.643 g KHP
KHP
1 mmol KHP  0.643 g KHP
1 mmol KHP 0.643 g
g KHP
% KHP =  100%  100%  72.7 %
g sample 0.884 g

18
Oxidation-Reduction
Reactions
• We have previously gone over the basic
concepts of oxidation & reduction in
Chapter 4.
• Rules for assigning oxidation numbers
were also introduced in Chapter 4.
– Refresh your memory as necessary.
• We shall learn to balance redox reactions
using the half-reaction method.
19
Balancing Redox Reactions
Half reaction method rules:
1. Write the unbalanced reaction.
2. Break the reaction into 2 half reactions:
One oxidation half-reaction and
One reduction half-reaction
Each reaction must have complete formulas for molecules
and ions.
3. Mass balance each half reaction by adding appropriate
stoichiometric coefficients. To balance H and O we can add:
 H+ or H2O in acidic solutions.
 OH- or H2O in basic solutions.

20
Balancing Redox Reactions
4. Charge balance the half reactions by adding
appropriate numbers of electrons.
 Electrons will be products in the oxidation half-
reaction.
 Electrons will be reactants in the reduction half-
reaction.
5. Multiply each half reaction by a number to make
the number of electrons in the oxidation half-
reaction equal to the number of electrons
reduction half-reaction.
6. Add the two half reactions.
7. Eliminate any common terms and reduce
coefficients to smallest whole numbers.

21
Balancing Redox Reactions
• Example 11-12: Tin (II) ions are oxidized to tin
Starting Reaction
(IV) by bromine. Use the half reaction method
to write and balance the net ionic equation.
Sn 2+
 Br  Sn
2
4+
 Br-

Mass
Massbalance thehalf
balance the half - reaction.
- reaction.
Sn2+2 +
Sn 4+ 4 +
SnSn
Charge balance the half - reaction.
Sn 2 +  Sn 4 +  2e -
Electrons are products thus this
is the oxidation half - reaction
22
Balancing Redox Reactions

22++
 4 +4 +
Sn  Sn  2e e
Sn Sn  2- -

Mass
Mass balance
balance thetheother
otherhalfhalf- reaction.
- reaction.
22Br
Br22 
Br Br - -

Charge balance the other half - reaction.

Br2  2e -  2 Br -
This is the reduction half reaction.
23
Balancing Redox Reactions

Sn Br
Br22  Sn 
2+ 4+ -
Sn 2+
 Sn Br
 Br 4+ - starting reaction
starting reaction
Add
Add the
the two
two half
half reactions.
reactions.
Sn  Sn  2e ox. half
22++ 44++ --
Sn Sn half reaction
reaction
Br22 22ee 
Br --
 2 Br red. half -
half reaction
reaction
Sn  Br2  Sn  2 Br balanced reaction
2+ 4+ -

24
Balancing Redox Reactions
• Example 11-13: Dichromate ions oxidize iron (II)
ions to iron (III) ions and are reduced to
chromium (III) ions in acidic solution. Write and
balance the net ionic equation for the reaction.
22
Cr222O
O777 
 Fe
Fe 22++

 Cr
Cr 3+
3+
 Fe
Fe 3+3+
startingreaction
starting reaction
Mass
Mass balance
balance thethehalf
half- reaction.
- reaction.
Fe 2 +
2+ 3+
Fe Fe
Fe3+
Charge balance the half - reaction.
Fe 2 +  Fe3+  1e 
Is this an oxidation or reduction half - reaction? 25
Balancing Redox Reactions
2
2
O7772 Fe
Cr222O Cr
Fe22++  Cr3+3+Fe Fe3+3+
startingrxnrxn
starting
Fe 22
2++
+

Fe  Fe + 1e Fe 3
3+
3+ +
+ 1e - -- oxidation
oxidation
oxidation
nd
Mass
Mass balance
Mass balance
balancethe the 2 ndnd
the22 ndhalf half -- reaction.
reaction
half- reaction
reaction
2
Cr
++ 2 OCr
H Cr O2 222 Cr

3+
2 3+37
Cr 3++H O
14
14 H Cr2 O
2O77  22Cr Cr  727HH2 OO
7
2 7 2

Charge balance the 2 nd half - reaction.

2
14 H +  Cr2 O 7  6 e -  2 Cr 3+  7 H 2 O

26
Balancing Redox Reactions

2
Cr2 O 7  Fe 2+  Cr 33++  Fe33++ start
start rxn
rxn
Multiply t heAdd
half the
- reactions
two halfto- reactions.
balance the electrons.

6 Fe 2+  Fe3+ + 1e --  ox.
ox.
2
Cr2 O 7  14 H +  6 e --  2 Cr 33++  77 H
H22O
O red.
red.
2
6 Fe 2+  Cr2 O 7  14 H +  6 Fe3+  2 Cr 3+  7 H 2 O

27
Balancing Redox Reactions
• Example 11-14: In basic solution hydrogen
peroxide oxidizes chromite ions, Cr(OH)4-,
to chromate ions, CrO42-. The hydrogen
peroxide is reduced to hydroxide ions.
Write and balance the net ionic equation
for this reaction.
You do it!

28
Balancing Redox Reactions


  2
2  2 22 2  2
Cr(OH)
Cr(OH)
Cr(OH)
Cr(OH)
Cr(OH) H
HHO
H
OO H
O 
4444 4 2 222222 22 2
2 O
CrO
CrO CrO
CrO 
CrO
24 44 44 4
(basic
(basic
(basic (basic
CrO solution)
solution)
solution)
(basic
(basic solution)
(basic
solution)
4 solution) solution)
st
2.
6.
1.
5.
3. Charge
Add
4.Mass
7. the
Balance
Charge
Mass balance
two
balance
Eliminate thethe
balance
balancethe
half
the 1-first
common
charge theonhalf
the nd -nd
reactions.
half ter
2both reaction.
-2reaction.
ms.
halfhalf
half reactions.
reaction.
- reaction.

Cr(OH)
Cr(OH)
2 Cr(OH)
Cr(OH)
Cr(OH)
2

 
 4
OH

4
44 4444 
Cr(OH) 4
OH
44OH
OH
OH
4
- - - --

OH -
CrO

CrO
CrO
-
 
CrO
4CrO
2
2 2 222
4 
H
4 4 4CrO
44
 4
2O
H
4

 +
H
4
44
2H3e
O
H
2 O
H
4 22 2
O+
O
O3e
++3e
4
+ H
3e 
2 - oxidation
- -- -
3e2 Oreaction
+ 3e -

3
H
H
3 HH22O2OO
2O
2 O
2 22
22
2eee- --
2 
2
OH2
2
22  2e  2OH  reduction reaction
- - ---
OH
OH
  2 2
Cr(OH)44 88OH
2 Cr(OH) OH- -33HH2 O
2O2 22 2
CrO 4 4 8
CrO H82H
O2+
O6OH -
+ 6OH -

 2
2 Cr(OH) 4  2OH-  3 H 2 O 2  2 CrO 4  8H 2 O

29
Balancing Redox Reactions
• Example 11-15: When chlorine is bubbled
into basic solution, it forms hypochlorite
ions and chloride ions. Write and balance
the net ionic equation.
You do it!
• This is a disproportionation redox reaction.
The same species, in this case Cl2, is
both reduced and oxidized.
30
Balancing Redox Reactions

     
Cl222
Cl
Cl ClO
 ClO
ClO
ClO  Cl
Cl
Cl(basic
Cl(basic(basic
solution)
(basic
(basic solution)
solution)
solution)
solution)
ndstnd st
6.
4.
5.
3.
1. Reduce
Charge
Add
Mass the to
two
balance smallest
balance the
half
the 2
2. Mass balancethethe 12- half whalf
half hole
reactions.
1half numbers.
- reaction.
--reaction.
reaction.
- reaction.
 
Cl
Cl 
4 OH
4
Cl 22222 4 4OH OH 
- - --
  
2 ClO2 
ClO
 2 H

 2 H O 
2 H2 e 
-
O  -
2 e -
22O22H
- -
Cl 4 OHOH 2
2 ClOClO
2 ClO 2 H O 2 e
2 2e2Ooxidation reaction
- - -
Cl 
2 2e Cl
Cl22  2 e  2 ClCl
Cl 2 e 
2 Cl2
  
reduction half - reaction
2

Cl
2 Cl 
2 2 24OH
OH
--

 ClO
2 ClO 
- -
Cl
2
-
Cl- H O
2
2 H 2O

31
Calculations for Redox
Titrations
• Just as we have done stoichiometry with
acid-base reactions, it can also be done with
redox reactions.
• Example 11-16: What volume of 0.200 M
KMnO4 is required to oxidize 35.0 mL of
0.150 M HCl? The balanced reaction is:

2 KMnO 4  16 HCl  2 KCl + 2 MnCl 2  5 Cl2  8 H 2O

You do it!
32
Calculations for Redox
Titrations
 35 mL HCl  0150
. M HCl  5.25 mmol HCl
 2 mmol KMnO 4 
 5.25 mmol HCl    0.656 mmol KMnO 4
16 mmol HCl 
 1 mL 
 0.656 mmol KMnO 4     3.28 mL
 0.200 mmol KMnO 4 

33
Calculations for Redox
Titrations
• Example 11-17: A volume of 40.0 mL of
iron (II) sulfate is oxidized to iron (III) by
20.0 mL of 0.100 M potassium dichromate
solution. What is the concentration of the
iron (II) sulfate solution? From Example
11-19 the balanced equation is:

2
6 Fe  Cr2 O7  14 H +  6 Fe3+  2 Cr 3+  7 H 2O
2+

You do it! 34
Calculations for Redox
Titrations

 20.0 mL   0.100 M Cr2O 7 2

  2.00 mmol Cr O
2 7
2

 
 
2+
6 mmol Fe
2.00 mmol Cr2 O 7  
2
2 
 12 .0 mmol Fe 2+

 1 mmol Cr2 O 7 
12.0 mmol Fe 2+
 0.300 M Fe 2+
40.0 mL

35
Synthesis Question
• A 0.7500 g sample of an impure FeSO4
sample is titrated with 26.25 mL of 0.0200
M KMnO4 to an endpoint. What is the %
purity of the FeSO4 sample?

36
Synthesis Question
molar mass of FeSO4  151.8 g mol  151.8 mg mmol
balanced redox reaction is :
MnO -4  8 H   5 Fe2  5 Fe3  Mn 2  4 H 2O
 26.25 mL  0.0200 M KMnO 4   0.525 mmol
 5 Fe2 
 0.525 mmol   
- 
 2 .625 mmol Fe 2

 1 MnO 4 

 2.625 mmol Fe2  11mmol

mmol
FeSO4  151.8 mg 
Fe 2  
mmol
  398.5 mg
  

 398.5 mg   1g 
  0.3985 g
 1000 mg 
0.3985 g
% purity   100%  53.13%
0.7500 g
37
Group Question
• Ice cubes that are made from water that is
found in limestone rich areas of the
country, such as Florida, have an unusual
property. When a soft drink,like Coca-
Cola, is poured over them an excessive
amount of “fizzing” occurs. Write the
molecular, total, and net ionic equations
for the reaction that causes the excessive
fizzing.
38
 Reactions in Aqueous
11 Solutions II:
Calculations

39