Cornered by Mike Baldwin

Announcement
Your midterm exam was returned to you. For those who
did not pick there exams, come to my office (when I am
there) and get it. I will not bring them to class anymore.
The solutions are now posted in the problem sets
section.

Dissociation of a weak acid in water

You must check your assumption

Find the equil. conc. in a solution of 1.0 M HCOOH.

Check if

H3O+ (aq) + HCOO (aq)

HCOOH (aq) + H2O (l)
K=

[H3O+][HCOO]
Ka
[HCOOH]

= 2.0 x 10
I
C
E

(acid dissociation const.)

0
+x
x

0.9859 1.000

0.9859

0
+x
x

x2
4
1 = 2.0 x 10

Remember approximation is OK when less than 5 %.

1.0 x 1.0
x = 0.0141 M

amount dissociated
Percent dissociation = initial concentration x 100%
0.0141 M
% dissociation = 1.0 M x 100% = 1.4%

Suppose

Notice that the % dissociation is very similar to the

error we calculated. Therefore calculating %
dissociation is a valid check provided it is less than 5%.

HA + H2O

x 100 % = 1.4% < 5%

Approximation acceptable and easier.

For a weak acid

valid

x2
K = 1.0 x = 2.0 x 104
Solve assuming

?
approx
x 100 % < 5%
real

In our case

(CDS T2)

1.0
x
1.0 x

real

% dissociation as it is diluted

H3O + A

Increase the dilution by adding water will shift

equilibrium towards the products (Le Chatelier) which
means greater dissociation.

[HCOOH]o = 0.5 M

H3O+ (aq) + HCOO (aq)

HCOOH (aq) + H2O (l)
I
0.5
C x
E 0.5 x

0
0 M
+x
+x
x
x
+

2
[H3O ][HCOO ]
x
x2
4
K = 2.0 x 10 = [HCOOH] = 0.5 x 0.5

Solve assuming
x2
4
0.5 = 2.0 x 10

0.5 x 0.5
x = 0.01 M

0.01 M
% dissociation = 0.5 M x 100% = 2 %

valid check

Compare with previous result, % dissociation increases

with lower concentration.

Checking approximations

Where does the 400 factor come from?

1) If

real

?
approx
x 100 % < 5%
real

valid

2) for weak acids and bases

5
1
5% is 100 or 20
calculations involve x2

?
If % dissociation < 5%

so need

1 2

20

1
= 400

valid

3) for weak acids and bases involving x2 calculations

?
If 400 Ka < initial concentration

valid

?
If 400 Kb < initial concentration

valid

You must always check your approximations. I will

penalize you in exams for not doing so.

In previous examples
400 Ka = 0.08 < 1.0

approximation is valid

< 0.5

approximation is valid

Dissociation of a weak base in water

Polyprotic acids

Find the equil. concentrations in 15.0 M NH3.

Several protons to donate

NH4+ (aq) + OH (aq)

NH3 (aq) + H2O (l)
I
15.0
0
0
M
C
x
+x
+x
E
15.0 x
x
x
14
2
Kw
10
x
5
Kb = K =
10 = 1.8 x 10 =
15.0 x
5.5 x 10
a

Examples: H2SO4 (very strong), H3PO4, H2CO3, etc.

H3PO4 + H2O

H2PO4 + H3O+

Ka1

H2PO4 + H2O

HPO42 + H3O+

Ka2

HPO42 + H2O

PO43

Ka3

assume 15.0 x 15.0

+ H3O+

x2
5
x = 0.0164 M
15.0 = 1.8 x 10
x = [OH]= [NH4+] = 0.0164 M

Ka1 > Ka2 > Ka3

[NH3] = 15.0 0.0164 = 14.98 M

H2SO4 + H2O HSO4 + H3O

check

400 Kb < 15

or check

0.0164
15.0 x 100 = 0.1%

The progressive acids become weaker and weaker

+

valid
valid

very strong acid

No value in CDS because dissociation is complete

SO42 + H3O+
HSO4 + H2O

K2 = 1.2 x 102

10

Calculate the pH of 2 M H2SO4 solution

Acid base properties of salt solutions

H2SO4 + H2O HSO4 + H3O

2.0

0.0

2.0

2.0

Salt = ionic solid

M

SO42 + H3O+
HSO4 + H2O
I

2.0

C
E

x
2.0 x

Examples: NaCl, K2CO3, Al(NO3)3

2.0

+x
x

+x
2.0 + x

(2 + x)x
K2 = 1.2 x 102 = (2 x)

Na+ (aq) + Cl (aq)

NaCl (s)

Salt solution acidic, basic or neutral ?

x = [SO42] = 1.2 x 102 M

1. Cation effect on pH

[H3O+] = 2 + 1.2 x 102 = 2.012 M

pH = 0.303

cation is not H , anion is not OH or O2.

2. Anion effect on pH

negative pH for strong concentrated

3. Combined effect of the cation and anion together

acids.

11

12

Cation effect

Anion effect

Cations derived from strong bases (group 1 + heavier

Anions derived from strong acids (Cl, Br, I, NO3,

group 2 cations) do not react with water no effect

ClO4, SO42) do not react with water no effect

+
Na+ + H2O NaOH + H Na+ + H2O

Cl + H2O HCl + OH Cl + H2O

NaOH is a strong base so it immediately dissociates to

HCl is a strong acid so it immediately dissociates to H+

Na+ and OH and the OH and H+ recombine to form

and Cl and the H+ and OH recombine to form H2O.

H2O. So no reaction for Na+ and water.

So no reaction for Cl and water.

All other cations react with water to yield weakly acidic

solutions.
+

NH4 , Transition metals, Al

NH4

+
(aq)

All other anions react with water to yield weakly basic

3+

H3O+ + NH3 (aq)

+ H2O

all weakly acidic

weakly acidic

solutions.
F (aq) + H2O

HF (aq) + OH (aq)

basic

13

14

Combined effect of cations and anions

Find the pH of a 1M NH4I solution

NH4I
Zn(NO3)2

Cation

Anion

acidic
acidic

-----------

Complete dissociation

acidic
acidic

I is derived from a very strong acid.

KClO4
Na3PO4

-----------

-----basic

neutral
basic

NH4F

acidic

basic

???

I + H2O

HI + OH

HI is a very strong acid and it immediately dissociates,

HI H+ + I

Rarely would the two effects exactly cancel each out

H+ + OH H2O

Ka(NH4+) = 5.5 x 1010

Net reaction: I + H2O

Kw
1 x 1014
= K (HF) = 7 x 104 = 1.4 x 1011
a

Kb(F )
+

Ka(NH4 ) > Kb(F )

When

I + H2O

no effect

Remember: ions derived from strong acids or strong

acidic

bases have no effect on the pH of the solution.

Ka > Kb

acidic

NH4+ is a weak acid and we need to consider its

Ka < Kb

basic

dissociation in water.

Ka = Kb

neutral

15

16

NH3 + H3O
NH4 + H2O
+

NH4I NH4+ + I

Overall

C x

+x

+x

E 1x

Ka (NH4 )
M

x2
x2
Ka (NH4+) = 5.5 x 1010 = 1 x 1
[H3O+] = x = 5.5 x 1010 = 2.35 x 105 M
pH = log (2.35 x 105) = 4.63
Check approximation
7

400 Ka = 2.2 x 10 < 1

valid

At home: Find the pH of a 1 M Na3PO4 solution.

Started in class and left for you to solve at home. The
solution provided here is so that you can check your
answer!
Na3PO4 3 Na+ + PO43
Group 1 salts tend to dissociate completely into ions.
HPO42 + OH

H2PO4 + OH
HPO42 + H2O
PO43 + H2O

H3PO4 + OH
H2PO4 + H2O
Kw
1014
Kb1 = K = 4.2 x 1013 = 0.0238
a3
Kw
1014
Kb2 = K = 6.3 x 108 = 1.59 x 107
a2
Kw
1014
Kb3 = K = 7.1 x 103 = 1.41 x 1012
a1

17

18

Kb1 >> Kb2 >> Kb3

Chapter 17, 18 Applications of aqueous equilibria

So can ignore contribution from the last 2 rxns

Common ion effect

HPO42 + OH
PO43 + H2O
I

+x

1x

Buffers
M

+x
x

x2
Kb (PO4 ) = 0.0238 = 1 x

Titrations

* done in the lab

Solubility equilibria
Complex ion equilibria

* Be warned that I will go through the concepts of

0.0238 0.0238 x = x

titrations in class but the lab is where youll do most of

x2 + 0.0238 x 0.0238 = 0

the calculations. You are still responsible for knowing

x1 = 0.143

x2 = ve

impossible !

[OH] = x = 0.143
pOH = log (0.143) = 0.85
pH = 14 0.85 = 13.15

basic as predicted

all titration calculations on my exams.