ACEE 219

E i
Environmental
t l Chemistry
Ch i t

Week
W k7
April 13, 2010
Innovation Hall 127
ACEE 219 Spring 2010 HDP 1
Review of Exam 1

ACEE 219 Spring 2010 HDP 2

 Diprotic Acid
pH
pKa1= 4.0 pKa2= 8.0
0 2 4 6 8 10 12 14
0

[A2-
2]
2 pCT,A = 2
[H2A]
n, pC

4
entration

[HA-]
6
og Conce

10
‐lo

12
[OH-] [H+]
14

ACEE 219 Spring 2010 HDP 3

Alpha Fraction (H2A)

[H2 A] [H+ ]2
α0 = = + 2
CT,A [H ] + [H+ ]K a,1 + K a,1K a,2

[[HA − ] [[H+ ]]K a,1

α1 = = + 2 a1

CT,A [H ] + [H+ ]K a,1 + K a,1K a,2

[A 2− ] K a,1K a,2
α2 = = + 2
CT,A [H ] + [H+ ]K a,1 + K a,1K a,2

ACEE 219 Spring 2010 HDP 4

 Carbonic Acid
10-5 M H2CO3*
pH
0 2 4 6 8 10 12 14
0

2
og Concentration, pC

4
[H2CO3*]
pCT,CO3 = 5
6

8
[HCO3-]
10
‐lo

12 [OH-] [H+]
[CO3 2-]

14
pKa1= 6.3 pKa2= 10.3
ACEE 219 Spring 2010 HDP 5
 Carbonic Acid
pH
0 2 4 5.7 6 7.6 8 9.0 10 12 14
0

2
og Concentration, pC

4
[H2CO3]
pCT,CO3 = 5
6

8
[HCO3-]
10
‐lo

12 [OH-] [H+]
[CO3 2-]

14

ACEE 219 Spring 2010 HDP 6

Mixtures of Acids and Bases
Estimation of pH for mixtures of acids and bases
: Many important analytical methods, natural processes, and treatment
schemes involve reactions between acids and bases

Strong acid-strong base Mixtures

(e.g.) HCl + NaOH, H2SO4 + NaOH

Weak
W k acid-strong
id t b
base and
d Strong
St acid-weak
id kbbase Mi
Mixtures
t
(e.g.) HAc + NaOH, HCl + NH3

ACEE 219 Spring 2010 HDP 7

 Example 4
4--24
Strong acid-strong base mixture
5 mL 0.1M NaOH addition to 1 liter of 10-3M HCl solution

Equilibrium
q
Kw = [H+][OH-] = 10-14
Mass balances

− number of moles 1 liter x10 -3 moles/lite r

CT,Cl = [Cl ] = =
total volume 1 liter + volume added
number of moles 0.1 moles/lite r x volume added
CT,Na = [Na + ] = =
total volume 1 liter + volume added
Charge balances
[Na + ] + [H+ ] = [Cl− ] + [OH− ]
Snoeyink & Jenkins Example 4-24

ACEE 219 Spring 2010 HDP 8

 Example 4
4--24
Strong acid-strong base mixture
− 10 -3
C T,Cl = [Cl ] = ≅ 10 -3 M
1 + 0.005
0.1
0 1 x 0.005
0 005
C T, Na = [Na + ] = ≅ 5 x 10-4 M
1 + 0.005

[Na + ] + [H + ] = [Cl − ] + [OH − ]

-3
10
5 x 10 -4 + [H + ] = 10-3 + +
[H ]
[H + ]2 − 5 x 10 -4 [H + ] - 10-14 = 0

+ 5 x 10 -4 + (5 x 10-4 ) 2 + 4 ⋅10-14
[H ] = = 5 x 10 -4
2
g[ + ] = 3.3
pH = - log[H
p

ACEE 219 Spring 2010 HDP 9

 Example 4
4--26
Weak acid-strong base mixture
5mL 0.1M NaOH addition to 1 liter of 10-3M HAc solution

Equilibrium
q [H+ ][Ac - ]
Kw = [H+][OH-] = 10-14 Ka = = 10 − 4.7
[HAc]

Mass balances
− number of moles 1 liter x10 -3 moles/lite r
CT,Ac = [HAC] + [Ac ] = =
total volume 1 liter + volume added
number of moles 0.1 moles/lite r x volume added
CT,Na = [Na + ] = =
total volume 1 liter + volume added
Charge balances
[Na + ] + [H+ ] = [Ac − ] + [OH− ]
Snoeyink & Jenkins Example 4-26

ACEE 219 Spring 2010 HDP 10

 Example 4
4--26
Weak acid-strong base mixture
− 10-3
C T, Ac = [HAc] + [Ac ] = ≅ 10-3 M
1 + 0.005
00.1
1 x 0.005
0 005
C T, Na = [Na + ] = ≅ 5 x 10-4 M
1 + 0.005

[Na + ] + [H + ] = [OH − ] + [Ac- ] = [OH − ] + C T, Ac ⋅ α1

10 -3
+ 10 − 4.7
5 x 10 + [H ] = + + 10 ⋅ +
-4 -3

[H ] [H ] + 10 − 4.7
[H + ] = 1.85x 10-5
pH = - log[H + ] = 4.73

ACEE 219 Spring 2010 HDP 11

 Titration
An acid-base titration is a method in chemistry that allows
quantitative analysis of the concentration of an unknown acid or
base solution. (Wikipedia)

http://water.me.vccs.edu/courses/ENV211/changes/titration.gif

ACEE 219 Spring 2010 HDP 12

 Titration
Indicator Colour on Acidic Side Range of Colour Change Colour on Basic Side

Methyl Violet Yellow 0.0 - 1.6 Violet

Bromophenol Blue Yellow 3.0 - 4.6 Blue

Methyl Orange Red 3 1 - 4.4

3.1 44 Yellow

Methyl Red Red 4.4 - 6.2 Yellow

Litmus Red 5.0 - 8.0 Blue

Bromothymol Blue Yellow 6.0 - 7.6 Blue

p
Phenolphthalein Colourless 8.3 - 10.0 Pink

Alizarin Yellow Yellow 10.1 - 12.0 Red

ACEE 219 Spring 2010 HDP 13

Strong Acid-
Acid-Strong Base
12

10

8
Equivalence Point
7.0
Equivalent of acid = Equivalent of base
pH

6
p

0
0 5 10 15 20 0.1M NaOH added (mL)
0 0.5 1.0 1.5 2.0 f, equivalent fraction

ACEE 219 Spring 2010 HDP 14

Strong Acid-
Acid-Strong Base

Na+ Na+

H+ Na+
Cl- Cl-

www.chembio.uoguelph.ca/.../titration_curves.htm

ACEE 219 Spring 2010 HDP 15

Weak Acid
Acid--Strong Base
12

10

Equivalence Point
8
78
7.8
pH

6
pKa=4.7
4

0
0 5 10 15 20 0.1M NaOH added (mL)
0 0
0.5
5 10
1.0 15
1.5 2
2.0
0
f, equivalent fraction

ACEE 219 Spring 2010 HDP 16

Weak Acid
Acid--Strong Base

www.chembio.uoguelph.ca/.../titration_curves.htm

ACEE 219 Spring 2010 HDP 17

 Comparison
12

10

7.8 Equivalence Points

8
70
7.0
pH

10-3 HAc 4

10-3 HCl 2

0
0 5 10 15 20 0.1M NaOH added (mL)
0 0.5 1.0 1.5 2.0
f equivalent fraction
f,

ACEE 219 Spring 2010 HDP 18

 pH Buffer
• Constant and well-regulated pH is essential for the proper functioning of the
many biological and chemical processes involved in water and wastewater
treatment.

• The most common method of preparing a buffered solution is to add a mixture

of a weak acid and its conjugate base.

• The pKa of the acid should be very close to the desired pH of the buffer solution
for maximum buffer intensity.

[base]
• pH = pK a + log
[acid]

ACEE 219 Spring 2010 HDP 19

 pH Buffer
C HA moles of HA + C NaA moles of NaA
Mass balance
C T, A = C HA + C NaA = [HA] + [A − ]
C T, Na = [Na + ] = C NaA
Charge balance
[Na + ] + [H + ] = [A − ] + [OH − ]

[A − ] = [H + ] - [OH − ] + [Na + ] = [H + ] - [OH − ] + C NaA

− − +
[HA] = C HA + C Na
NaA − [A ] = C HA + [OH ] - [H ]

+ (C HA + [OH − ] - [H + ])
[H ] = K a
(C NaA - [OH − ] + [H + ])
C HA
[H + ] = K a
C NaA
⎛C ⎞ [base]
pH = pK a + log⎜⎜ NaA ⎟⎟ pH = pK a + log
⎝ C HA ⎠ [acid]
ACEE 219 Spring 2010 HDP 20
 pH Buffer
Buffer Intensity (β)

The mole/liter of strong base (CB) or OH- which when added to a solution
cause a unit change in pH
dC B dC A
β= =−
dpH dpH

Example 4-28

1 Determine which acid

1. acid-conjugate
conjugate base should be used to buffer a solution
at (i) pH 4.7 and (ii) pH 7.0. What ratio of acid to conjugate base should
be used in each of these buffers?

2. What is the pH of each of these buffers after addition of 10-4 mole of

NaOH per liter of solution if CT = 10-3 M in each case?
Snoeyink & Jenkins Example 4-28

ACEE 219 Spring 2010 HDP 21

Titration--Water
Titration

http://www.advancedaquarist.com/2
002/2/ h i t
002/2/chemistry_album/figure1.gif
lb /fi 1 if

ACEE 219 Spring 2010 HDP 22