Chem2000 Spring 2004

Assignment 3 Friday January 30, 2003

1) The pH of 0.040 M HOBr is 5.050. Calculate the acidity constant, Ka, the basicity
constant Kb, and the % dissociation.

HOBr + H2O U OBr - + H3O+

I 0.040 0.00 0.00
-x +x +x
E 0.040 x x x

x = [H3O+] = 10-pH = 10 5.050 = 8.913 * 10 6 M

Ka = [H3O+][ OBr -]/[ HOBr]

= (8.913 * 10 6) (8.913 * 10 6)/ 0.040 8.913 * 10 6)

= 1.99 * 10 9

Kb = Kw/Ka = 5.09 * 10 6

% dissociation = (8.913 * 10 6)*100/ 0.040 = 0.022 %

2) Phenol (C6H5OH) is a weak acid used as a general disinfectant. Calculate the pH and the
concentrations of all species present in a 0.10 M solution of phenol ( C6H5OH, C6H5O- ,
H3O+, and OH-). Phenol has Ka = 1.3 * 10 10. Compute the % dissociation of phenol in
this solution and of a 1000 times dilution of this solution (i.e.0.00010 M phenol).

C6H5OH + H2O U C6H5O - + H3O+

I 0.10 0.00 0.00
-x +x +x
E 0.10 x x x

Ka = 1.3 * 10 10 = x2/(0.10 x)

Assume x <<0.10 => 1.3 * 10 10 = x2/(0.10 )

x2 = 1.3 * 10 11 x = 3.61 *10-6 M = [H3O+]

pH = 5.44

% diss. = [H3O+] * 100/[C6H5OH]o = (3.61* 10-6)100/0.10 = .0036 %

 1000 times dilution

C6H5OH + H2O U C6H5O - + H3O+

I 0.00010 0.00 0.00
-x +x +x
E 0.00010 x x x

Ka = 1.3 * 10 10 = x2/(0.00010 x) assume x << 0.00010

1.3 * 10 14 = x2/0.00010

1.3 * 10 14 = x2

x = 1.14 * 10 7 = [H3O+] pH = 6.943

% diss = (1.14 * 10 7)*100/ 0.00010 = 0.114 %

3) Morphine (C17H19NO3) is a narcotic used in painkillers as a weak base. If the pH of a

7.0* 104 M solution of morphine is 9.50, determine Kb, Ka, and % dissociation.

C17H19NO3 + H2O U C17H20NO3+ + OH-

I 0.00070 0.00 0.00
-x +x +x
E 0.00070 x x x

x =[OH-] = Kw/ [H3O+] = Kw/10-pH = 1.01 * 10-14/ 10 9.50 = 3.19 * 10-5 M

Kb = [C17H20NO3+][OH-]/[C17H19NO3] = (3.19*10-5)2/(0.00070 3.19*10-5)

Kb = 1.52 * 10 6

Ka = Kw/Kb = 1.01 * 10-14/ 1.52 * 10 6 = 6.63 * 10 9

% diss = [OH-]*100/[ C17H19NO3]o = (3.19 * 10-5)* 100/(0.0007) = 4.55 %

4) Aniline (C6H5NH2) is an organic base used in the manufacture of dyes. Calculate the pH
and concentrations of all species present (C6H5NH2, C6H5NH3+, OH- and H3O+) in a 0.15
M solution of aniline, Kb = 4.3 * 1010. Compute % dissociation aniline in this solution
and in a 1000 times dilution of this solution.( i.e. 0.00015 M aniline).

C6H5NH2 + H2O U C6H5NH3+ + OH-

I 0.15 0.00 0.00
-x +x +x
E 0.15 x x x

Kb = 4.3 * 1010 = x2/(0.15 x) assume x << 0.15

4.3 * 1010 = x2/(0.15)

6.45 * 10 11 = x2 => x = 8.03 * 10 6 M = [OH-]

pOH = 5.10 pH = 14.00 5.10 = 8.90

% diss = [OH-]*100/[ C6H5NH2] = (8.03 * 10 6) * 100/0.15 = 0.0053 %

1000 times dilution

C6H5NH2 + H2O U C6H5NH3+ + OH-
I 0.00015 0.00 0.00
-x +x +x
E 0.15 x x x

Kb = 4.3 * 1010 = x2/(0.00015 x) assume x << 0.00015

4.3 * 1010 = x2/(0.00015)

6.45 * 10 14 = x2 => x = 2.54 * 10 7 M = [OH-]

pOH = 6.60 pH = 14.00 6.60 = 7.40

% diss = [OH-]*100/[ C6H5NH2]

= (2.54 * 10 7) * 100/0.00015 = 0.169 %

5) Three solutions are prepared each contains one of methyl red, methyl orange and
phenolphthalein. Determine the color of each solution at the following pH values: 2, 4, 6,
8, 10. Methyl red is red in its acidic form and yellow in its basic form and has a Ka = 2.5
* 10-6. Methyl Orange is orange in its acidic form and yellow in its basic form and has a
Ka = 1.6 * 10-4. Phenolphthalein is colorless in its acidic form and violet in its basic
form and has a Ka = 7.9 * 10-10.

________________________________________________________________________
pH Methyl Red Methyl Orange Phenolpthalein
(pKa = 5.60) (pKa=3.80) (pKa=9.10)

HIn or In- Colour HIn or In- Colour HIn or In- Colour

________________________________________________________________________
2 HIn Red HIn Orange HIn Clear

4 HIn Red Both Mixed HIn Clear

(Y and O)
6 Both Mixed In- Yellow HIn Clear
(R and Y )

8 In- Yellow In- Yellow Mixed light

HIn violet
dominates

0 In- Yellow In- Yellow

Mixed violet
-
In
dominates
________________________________________________________________________

6) Sulfur dioxide, SO2, is soluble in water:

SO2(g) + H2O(l) U H2SO3(aq) K= 1.33

The H2SO3 produced is a weak diprotic acid with Ka1 = 1.5 * 10 2 and Ka2 = 6.3 * 10 8.

H2SO3 + H2O(l) U HSO3-(aq) + H3O+(aq) Rnx (1)

HSO3- + H2O(l) U SO32-(aq) + H3O+(aq) Rnx (2)

Calculate the pH and the concentration of H2SO3, HSO3-, SO32- in a solution prepared by
continuously bubbling SO2 at a pressure of 1.00 atm. in pure water.
Assume that the SO2 gas H20 liquid equilibrium dominates and hence determines the
initial concentration of H2SO4 in solution.

K = 1.33 = [H2SO3]/PSO2 (M/atm)

[H2SO3] = K* PSO2 = (1.33 M/atm)*(1.00 atm) = 1.33 M

This concentration will be maintained throught out since any loss to further
dissociation reaction will cause the first reaction to produce more. Now assume that the
second dissociation will not affect the H3O+ concentration.

H2SO3 + H2O(l) U HSO3-(aq) + H3O+(aq)

I 1.33 M
x +x +x
E 1.33 M x x
(Kept constant)

Ka1 = [HSO3-][ H3O+]/[ H2SO3] = x2/(1.33) = 1.5 * 10 2

x2 = 2.0 * 10 2 => x = 0.14 M

[ H3O+] = 0.14 M these will serve as initial concentrations

[HSO3-] = 0.14 M for the second dissociation equilibrium.

HSO3- + H2O(l) U SO32-(aq) + H3O+(aq)

I 0.14 M 0.00 0.14
x +x +x
E 0.14 - x x 0.14 + x

Ka2 = [SO32-][ H3O+]/[ HSO3-] = x(0.14 + x)/(0.14 -x) = 6.3 * 10 8

Assume x is very small

x(0.14 + x)/(0.14 -x) x(0.14)/(0.14) = x = 6.3* 10 8 M

x = [SO32-] = 6.3* 10 8 M

[H3O+] = 0.14 + 6.3* 10 8 = 0.14 M pH = 0.85

7) Why is a solution of NaF basic, whereas a solution of NaCl is neutral. Show all relevant
acid-base equations to support your answer.

NaF(aq) U Na+(aq) + F-(aq)

Na+ is a conjugate acid of a very strong base (NaOH), and hence it is a very weak acid,
which does not undergo hydrolysis.

F- is the conjugate base of a weak acid (HF) and is therefore a relatively strong acid,
which does undergo hydrolysis reactions, producing OH- causing the pH to increase.

NaCl(aq) U Na+(aq) + Cl-(aq)

Na+ does not change pH of solution as before.

Cl- is the conjugate base of an extremely strong acid (HCL) and therefore is an extremely
weak base which does nor undergo hydrolysis reaction. The pH of this solution does not
change.

8) Explain with acid-base equations whether an aqueous solution of each of the following
salts will be acidic, basic or neutral.

a) SrBr2(aq) U Sr2+(aq)+ 2Br2(aq)

Br is the conjugate base of an extremely strong acid (HBr) and therefore an

extremely weak base => no hydrolysis

Sr2+ is a conjugate acid of a very strong base (Sr(OH)2), and therefore an

extremely weak acid => no hydrolysis

Solution is neutral.

b) Ba(CH3COO)2 U Ba2+(aq) + 2 CH3COO- (aq)

CH3COO- is the conjugate base of an weak acid (CH3COOH) and therefore is a an

effective base => hydrolysis => raised pH

Ba2+ is a conjugate acid of a very strong base (Ba2+(OH)2), and therefore an

extremely weak acid => no hydrolysis

Solution is basic.
c) (CH3)NH2Br (aq) U (CH3)NH2+(aq) + Br-(aq)

Br- is the conjugate base of an very strong acid (HBr) and therefore is a an
ineffective base => no hydrolysis

(CH3)NH2+ is a conjugate acid of a weak base ((CH3)NH), and therefore is a

effective acid => hydrolysis => pH is lowered.

Solution is acidic.

d) KBr (aq) U K+(aq) + Br-(aq)

Br is the conjugate base of an extremely strong acid (HBr) and therefore an

extremely weak base => no hydrolysis

K+ is a conjugate acid of a very strong base (KOH), and therefore an extremely

weak acid => no hydrolysis

Solution is neutral.

e) NH4I (aq) U NH4+(aq) + I-(aq)

I is the conjugate base of an extremely strong acid (HI) and therefore an

extremely weak base => no hydrolysis

NH4+ is a conjugate acid of a weak base (NH3), and therefore is a effective acid
=> hydrolysis => pH is lowered.

The solution is acidic.

f) KCN(aq) U K+(aq) + CN-(aq)

K+ is a conjugate acid of a very strong base (KOH), and therefore an extremely

weak acid => no hydrolysis

CN- is the conjugate base of an weak acid (HCN) and therefore is a an effective
base => hydrolysis => raised pH

This solution is basic

9) What is the pH of a buffer consisting of 0.20 M NH3 and 0.10 M NH4Cl (Kb for NH3 is
1.78*10-5).

NH4+(aq) + H2O (aq) U H3O+(aq) + NH3 (aq)

Using the Henderson Hasselbach Equation:

pH = pKa log ([Acid]o/[Base]o)

pKa = pKw pKb = 14.00 - -(log(1.78*10-5)) = 9.25

[Acid]o = [NH4+]o = 0.10 M

[Base]o = [NH3]o = 0.20 M

pH = 9.25 log(0.10/0.20) = 9.55

10) What is the buffer-component ratio [NO2-]/[HNO2] of a buffer that has pH of 2.95 where
Ka for HNO2 is 7.1*10-4.

Using the Henderson Hasselbach Equation:

pH = pKa log ([Acid]o/[Base]o)

pH = pKa log ([HNO2]/[NO2-])

2.95 = -log(7.1*10-4) log ([HNO2]/[NO2-])

2.95 = 3.15 log ([HNO2]/[NO2-])

2.95 3.15 = -0.20 = log ([HNO2]/[NO2-])

([HNO2]/[NO2-] = 10 0.20 = 1.58

[NO2-]/[HNO2] = 0.63

11) A buffer is prepared by mixing 184 ml of 0.442 M HCl and 0.500 L of 0.400 M
Na+CH3COO-, where Ka = 1.8 * 10 5. Determine the pH. How many grams of KOH
must be added to 0.500 L of buffer to change the pH by 0.15 units?

noH3O+ = (0.442 M) * (0.184) = 0.0813 mol HCl added.

noCH3COO- = (0.400 M) *(0.500 L) = 0.200 mol Na+CH3COO- added.

 Total Volume = 0.184 L + 0.500 L = 0.684 L
The amount of CH3COOH produced upon adding HCl to sodium acetate is determined
by the amount of acid added, since nearly all the H3O+, from adding HCl, will be
consumed to produce the acid form.

nCH3COOH = noH3O+ = 0.0813 mol

The amount of acetate remaining is therefore the amount in excess to that of the HCl
added.

nCH3COO- = noCH3COO- - noH3O+ = 0.200 - 0.0813 mol = 0.119 mol

[CH3COOH]o = (0.0813 mol)/(0.684 L) = 0.119 M

[CH3COO-]o = (0.119 mol)/(0.684 L) = 0.174 M

Using the Henderson Hasselbach Equation:

pH = pKa log( [CH3COOH]o /[CH3COO-]o)

pH = -log(1.8*10-5) log(0.119/0.174) = 4.74 0.17= 4.91

Addition of x grams of NaOH will decrease [CH3COOH]o and increase [CH3COO-] by:

x/(MW(NaOH)*Volume) call this y

pH(before) = pKa log([CH3COOH]o/[CH3COO-])

pH(after) = pH(before) + 0.15 = pKa log{([CH3COOH]o-y)/([CH3COO-]+ y)}

pH(after) pH(before) = 0.15 = log{([CH3COOH]o-y)/([CH3COO-]+ y)}-

( log([CH3COOH]o/[CH3COO-]))

-0.15 = log{(([CH3COOH]o-y) [CH3COO-]o))/{([CH3COO-]o + y) [CH3COOH]o}

10-0.15 = ([CH3COOH]o-y) [CH3COO-]o)/( ([CH3COO-]o + y) [CH3COOH]o)

0.708 = (0.119 y)( 0.174)/(( 0.174 + y)(0.119))

0.484 = (0.119 y)/( 0.174 + y)

0.0842 + 0.484y = 0.119 - y

1.484y = 0.0348

y = 0.0234 M

MW(NaOH) = 39.098 + 15.999 + 1.008 = 56.105 g/mol

y = x/(MW(KOH)*V)

0.0234 = x/(56.105*0.500)

x = 0.66 g