ACEE 219

E i
Environmental
t l Chemistry
Ch i t

Week
W
k5
March 30, 2010
Innovation Hall 127
ACEE 219 Spring 2010 HDP

pC--pH Diagram
pC

pC-pH diagram for 10-3 moles of HCN to 1 liter of pure water.

1. Mass balance on CN
CT,CN = [HCN] + [CN-] = 10-3
2. Equilibrium relationships
Kw = [H+][OH-] = 10-14

[H+ ][CN- ]
Ka =
= 10 9.3
[HCN]
3. Charge balance, Proton condition
[H+] = [CN-] + [OH-]

ACEE 219 Spring 2010 HDP

pC--pH Diagram
pC
pH
0

10

12

14

llogConcentration
n,pC

Line 1 (pCT - pH)

- logCT,CN
T CN = pCT,CN
T CN = 3

10

12

14

ACEE 219 Spring 2010 HDP

pC--pH Diagram
pC
pH
0

10

12

14

Line 2 (pOH - pH)

llogConcentration
n,pC

-logKw = -log[H+] - log[OH-]

14 = pH + pOH
6

pOH = 14 - pH

10

12

14

ACEE 219 Spring 2010 HDP

pC--pH Diagram
pC
pH
0

10

12

14

llogConcentration
n,pC

Line 3 (pH - pH)

- log[H+] = pH

10

12

14

ACEE 219 Spring 2010 HDP

pC--pH Diagram
pC
pH
0

10

12

14

llogConcentration
n,pC

Line 4 (pCN - pH)

when Ka >> [H+] (i.e., pH > pKa)

[[CN ] = 1 C T,CN

=
10

Ka
C T,CN
[H+ ] + K a

[CN ] = C T,CN = 10 3

12

p[CN ] = 3

14

ACEE 219 Spring 2010 HDP

pC--pH Diagram
pC
pH
0

10

12

14

llogConcentration
n,pC

[CN ] = 1 C T,,CN

[CN ] =

10

Ka
C T,CN
+
[H ] + K a
Ka
C T,CN
[H+ ]

p[CN ] = pK a pH + pC T,,CN
= 12.3 - pH

12

14

Li 5 (pCN
Line
( CN - pH)
H)
when Ka << [H+] (i.e., pH < pKa)
ACEE 219 Spring 2010 HDP

pC--pH Diagram
pC
pH
0

10

12

14

Line 6 (pHCN - pH)

when Ka << [H+] (i.e., pH < pKa)

llogConcentration
n,pC

[HCN] = 0 C T,CN
[H+ ]
= +
C T,CN
[H ] + K a

[HCN] = C T,CN = 10 3
p[HCN] = 3

10

12

14

ACEE 219 Spring 2010 HDP

pC--pH Diagram
pC
pH
0

10

12

14

Line 7 (pHCN)
when Ka >> [H+] (i.e., pH > pKa)

llogConcentration
n,pC

[HCN] = 0 C T,,CN

[H+ ]
= +
C T,CN
[H ] + K a

[H+ ]
C T,CN
[HCN] =
Ka

10

p[CN ] = ppH - pK a + pC T,
p[
T CN
= pH - 6.3

12

14

ACEE 219 Spring 2010 HDP

pC--pH Diagram
pC
pH
6

logConccentratio
on,pC

2
2.5

pKa

10

11

12

1.0 unit left pKa 1.0 unit right pKa

0.3 unit below CT

33
3.3

3.5

logCT = log([CN]+[HCN])
= log2[HCN]

4.5
5

log[HCN] = logCT - log2

= - 3 -log2 = -3.3

5.5
6

8.3

9.3

10.3

ACEE 219 Spring 2010 HDP

10

pC--pH Diagram
pC
pH
0

pKa = 9.3
93
8

10

12

14

llogConcentration
n,pC

pCT,CN = 3
4

[HCN]
6

[CN-]

10

[OH-]

[H+]

12

14

ACEE 219 Spring 2010 HDP

11

How to determine Eq. pH

using pCpC-pH diagram
Find pH (or pOH) where the proton condition or charge balance
is satisfied.

pH
0

logConcentraation,pC
C

[H+]

10

12

14

[OH-]

Example 4-16

2
4

[HCN]

[CN-]

10-3 M HCN
Proton condition:

[H+] = [CN-] + [OH-]

8
10
12
14

6.2 (equilibrium pH)

ACEE 219 Spring 2010 HDP

12

How to determine Eq. pH

using pCpC-pH diagram
Find pH (or pOH) where the proton condition or charge balance
is satisfied.

pH
0

logConcentraation,pC
C

[H+]

10

12

14

[OH-]

Example 4-17

2
4

[HCN]

[CN-]

10-3 M NaCN
Proton condition:

[HCN] + [H+] = [OH-]

8
10
12
14

10.1 (equilibrium pH)

ACEE 219 Spring 2010 HDP

13

HOCl
Draw a pC-pH diagram for 1.5x10-4 moles of HOCl to 1 liter of pure water.
1. Mass balance on OCl
CT,OCl = [HOCl] + [OCl-] = 1.5x10-4 (pCT,OCl = 3.8)
2. Equilibrium relationships
Kw = [H+][OH-] = 10-14

[H+ ][OCl- ]
Ka =
= 10 7.5
[HOCl]
3. Charge balance, Proton condition
[H+] = [OCl-] + [OH-]

ACEE 219 Spring 2010 HDP

14

HOCl
pH
0

pKa = 7.5
8

10

12

14

logConc
centratio
on,pC

pCT,CN = 3.8

[OCl-]

[HOCl]

[H+]

10

12

[OH-]

14

ACEE 219 Spring 2010 HDP

15

HOCl
pH
0

logConcen
ntration,,pC

[H+]

10

12

14

[OH-]

1 5 x 10-4 M HOCl
1.5

Proton condition:
6
8

[HOCl]

[H+] = [OCl-] + [OH-]

[OCl-]

How about 1.5 x 10-4 M NaOCl ?

10
12
14

5 7 (equilibrium pH)
5.7
ACEE 219 Spring 2010 HDP

16

Multiprotic Acid
Example
Draw a pC-pH diagram for 10-2 moles of H2A to 1 liter of pure water.
1 M
1.
Mass b
balance
l
on OCl
CT,A = [H2A] + [HA-] + [A2-] = 10-2 (pCT,A = 2)
2 E
2.
Equilibrium
ilib i
relationships
l ti
hi
Kw = [H+][OH-] = 10-14

[[H+ ][
][HA - ]
K a,1 =
= 10 4
[H2 A]
K a,2
a2

[H+ ][A 2- ]
8
=
=
10
0
[HA - ]

3. Charge Balance
[H+] = [OH-] + [HA-] + [A2-]
ACEE 219 Spring 2010 HDP

17

Multiprotic Acid
0

pKa1= 4.0
4

pH
6

pKa2= 8.0
8

10

12

14

2]
[A2-

pCT,A = 2

lo
ogConce
entration
n,pC

[H2A]
4

[HA-]
6

10

12

[OH-]

[H+]

14

ACEE 219 Spring 2010 HDP

18

Multiprotic Acid
pH
0

logConce
entration
n,pC

0
2

10

[H+]
[H2A]

12

14

[OH-]
[A2-]

[HA-]

Example 4-20 (1)

10-2 M H2A
Proton condition:

[H+] = [HA-] + 2[A2-] + [OH-]

10
12
14

3.05 (equilibrium pH)

ACEE 219 Spring 2010 HDP

19

Multiprotic Acid
pH
0

logConce
entration
n,pC

0
2

[H+]
[H2A]

10

12

14

[OH-]
[HA-]

[A2-]

Example 4-20 (1)

10-2 M Na2A
Proton condition:

2[H2A] + [HA-] + [H+] = [OH-]

10
12
14

10 (equilibrium pH)

ACEE 219 Spring 2010 HDP

20

Summary for the Exam1

1. Features of Water
2 Rate laws (0
2.
(0, 1st, 2nd order chemical kinetics)
3. Arrhenius equation
4 Biological
4.
Bi l i l ki
kinetics
ti
5. Chemical equilibrium
6. Gibbs free energy
7. Equilibrium constant & effect of temperature on K
8. Numerical and graphical methods for estimating
acid and base equilibrium concentrations.
ACEE 219 Spring 2010 HDP

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