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Chemical Equilibrium
Consider these
equilibrium eqn for
mbe and cbe:
NaHCO3 = Na+ +
HCO3HCO3- + H2O = H2CO3 +
OH18 Acid-Base Equilibria
-
2-
Charge balance in
a solution that
contains 0.0250 M
KH2PO4 and
0.0300 M KOH.
The sum of
positive charges =
sum of negative
charges.
H3NCH2CO2- H2NCH2CO2- + H+
M = [Mg2+] + [MgOH+],
Therefore X = 2([Mg2+] + [MgOH+]) + [H+];
Hydroxide X in solution exits in the forms of [OH-] and [MgOH+],
X = [OH-] + [MgOH+],
Combined the above steps: [OH-] + [MgOH+] = 2([Mg2+] +
[MgOH+]) + [H+];
First: the calcium oxalate should not bear no charge, as pointed out by a
student in class. If so, the charge balance equation will be
2[Ca2+] = 2[C2O42-] + [HC2O4-] + [OH-]
Assuming the original question is correct, the charge balance equation
would be 2[Ca2+] = 2[C2O42-] + [HC2O4-] + [OH-] + 2[CaC2O42-]
If we also consider the autoprotolysis of H2O: H2O H+ + OH(R1)
The charge balance equation will become
2[Ca2+] + [ H+] = 2[C2O42-] + [HC2O4-] + [OH-]
MULTIPLE CHEMICAL
EQUILIBRIUM
Equilibrium Calculations
Previous
BaC2O4 Ba2+ + C2O42[Ba2+] = [C2O42-]
27
Systematic Treatment of
Equilibrium
How does the solubility of CaF2 depend on pH?
CaF2(s) Ca2+ + 2F-
F-+H2O HF + OH-
[HF][OH ]
11
Kb
1
.
5
10
[F ]
H2O H+ + OH-
Kw = [H+][OH-] = 1.010-14
(1)
(2)
(3)
28
[HF][OH ]
11
Kb
1
.
5
10
[F ]
Kw = [H+][OH-] = 1.010-14
(1)
(2)
(3)
(4)
(5)
1
.
5
10
[F ]
Kw = [H+][OH-] = 1.010-14
K b [F ]
2
[F ]
2
[
Ca
]
[OH ]
2
2
[
Ca
]
[F ]
Kb
1
[OH ]
(B)
31
Solving
the
Equations
(B)
Combine (B) and eq. 1, we have
2[Ca ]
[F ]
Kb
1
[OH ]
(C)
K sp
Kb
1
[Ca ]
[OH ]
4
1
3
K sp
2
2[Ca ]
[Ca 2 ]
Kb
1
[
OH
]
If we can fix pH
pH = 3.00
[H+] = 1.010-3 M
Kw
[OH-] = 1.010-11 M
Kb
[HF-] =1.5[F-]
Mass
[Ca2+] = 3.910-4 M
[F-] =0.80[Ca2+]
Ksp
F-
4x10-11 = s (2s)2
s = 2x10-4
System: Closed
Components: HA & H2O
Species: HA, A-, H2O, OH-, H+
Equilibria: H2O = H+ + OH-
Kw = [H+][OH-] = 10-14
HA = H+ + AKA = [H+][A-]/[HA] = 10-6
Mass Balance: AT = [HA] + [A-] = 10-3 M
Charge Balance: [A-] + [OH-] = [H+]
Summary of steps
Plot line for [H+]: pH = pH
Plot line for [OH-]: pOH = pKW -pH
Plot AT: horizontal line at pC = pAT
Plot system point: pH = pKA on pAT line
Plot AT
System
point
AT
H A
[ HA]
K H
In log form
log[ HA] log H log A log K H
T
pH dependence of pHA
HA
[A ]
KA H
In log form
log[ A ] log AT
Complete system
Intercep
t ~ 0.3
log
below AT
CT
NUMERICAL EQUILIBRIUM
CALCULATIONS
Monoprotic acid
What are the pH and the
concentrations of all aqueous
species in a 5 x 10-4 M solution of
aqueous boric acid (B(OH)3)?
Steps to solution
1) Write down all species likely to be
present in solution: H+, OH-,
B(OH) 0, B(OH) -.
58
[ H ][ B (OH ) ]
10
(ii)
KA
7
x
10
[ B (OH ) 30 ][ H 2O]
59
60
Kw
[H ]
[ H ] [ B (OH ) 4 ]
(v)
61
[ H ][ B (OH ) ]
KA
B [ B (OH ) ]
62
63
[OH-] = Kw/[H+]
[OH-] = 10-14/10-6.21
[OH-] = 10-7.79 M
[B(OH)4-] = [H+] - Kw/[H+]
[B(OH)4-] = 6.1x10-7 - 1.62x10-8
[B(OH)4-] = 5.94x10-7 M
[B(OH)30] = B - [B(OH)4-]
[B(OH)30] = 5x10-4 - 5.94x10-7 M = 4.99x10-4 M
64
APPROXIMATE SOLUTION
Look for terms in additive equations
that are negligibly small
(multiplicative terms, even if very
small, cannot be neglected.
Because we are dealing with an acid,
we can assume that [H+] >> [OH-] so
that the mass balance becomes:
[H+] = [B(OH)4-]
and then
[B(OH)30] = B - [H+]
65
[ H ][ B (OH ) 4 ]
10
KA
7
x
10
[ B (OH ) 30 ][ H 2O]
(ii)
[ H ]2
KA
B [ H ]
[H+]2 = KAB-KA[H+]
[H+]2 + KA[H+] - KAB = 0
This is a quadratic equation of the form:
ax2 + bx + c = 0
and can be solved using the quadratic equation
b b 4ac
x
2a
2
66
K
A
A 4 K A B
[H ]
2
[ H ][ B (OH ) 4 ]
10
KA
7
x
10
[ B (OH ) 30 ][ H 2O]
[ H ]2
10
KA
7
x
10
[ B (OH )30 ]
[ H ]2
10
KA
7
x
10
5 x10 4
[ H ][OH ]
[
H
][
Cl
]
14
3
Kw
10
KA
10
[ H 2O ]
[ HCl 0 ]
3) Mass balance: [HCl0] + [Cl-] = 2 x 10-4 M
4) Charge balance: [H+] = [Cl-] + [OH-]
69
+
-14
-4 4 2
-11
[OH-][ H= ][KCl
/[H
]
=
10
/2
x
10
=
5
x
10
M
]
(
2
x
10
)
w
3
0
11
KA
10
[ HCl ]
4 x10 M
0
3
[ HCl ]
10
70
[ H ][ Ac ]
4.70
KA
10
[ HAc 0 ]
[ H ][OH ]
Kw
10 14
[ H 2O]
[ H ][ Ac ]
4.70
KA
10
[ HAc 0 ]
[ H ]C
KA
Kw
[
H
]
[H ]
72
74
CALCULATE THE pH OF AN
AMPHOLYTE
Calculate the pH of a 10-3.7 M solution of
sodium hydrogen phthalate (NaHP). COOH
1) Species: H2P0, HP-, P2-, H+, OH-, Na+ COONa
2) Mass action expressions:
K A,1 10 2.95
[ H ][ HP ]
[H 2 P0 ]
K A, 2
2
[
H
][
P
]
5.41
10
[ HP ]
[ H ][OH ]
Kw
10 14
[ H 2O ]
PT = 10-3.7 M = [Na+]
4) Charge balance:
[H+] + [Na+] = [OH-] + [HP-] + 2[P2-]
Now, substitute 3) into 4) to get proton
condition:
[H+] + [H2P0] + [HP-] + [P2-] = [OH-] + [HP-] +
2[P2-]
[H+] + [H2P0] = [OH-] + [P2-]
Because both pK values are less than 7,
assume:
[OH-] << [H+]
[H+] + [H2P0] = [P2-]
76
2
K
[
HP
]
A, 2
[ H ] PT
[
HP
]
[H ]
2 K A, 2
[ H ] PT
1
[
HP
]
[H ]
[ HP ]
[ H ] PT
2 K A, 2
1
[H ]
PT [ H 2 P 0 ] [ HP ] [ P 2 ]
[
HP
]K A , 2
[ HP ][ H ]
PT
[ HP ]
K A,1
[H ]
[H ]
K A, 2
PT
1 [ HP ]
[H ]
K A,1
77
[H ]
K A, 2 [ H ] PT
PT
1
2 K A, 2
K
[
H
]
A
,
1
[H ]
[H ]
K A, 2
[
H
]
P
T
T
[H ]
[
H
]
A,1
2 K A, 2 PT
PT K A, 2
[ H ]2
P
[
H
]
T
PT
[ H ] K A, 2
PT
[H ]
K A,1
K A,1
[H ]
2 K A, 2 PT
2
[ H ]3
P
[
H
]
2
T
2 K A, 2 PT
[ H ] K A, 2 [ H ]
PT K A, 2
K A,1
K A,1
78
PT [ H ] PT K A, 2 K A,1
[ H ]3 ( K A,1 PT )[ H ]2 K A, 2 K A,1[ H ] K A, 2 K A,1 PT 0
79
CALCULATION OF THE pH OF A
POLYPROTIC ACID
Compute the pH and concentrations of all species
in equilibrium in a 10-3 M H3PO4 solution.
1) Species: H+, OH-, H3PO40, H2PO4-, HPO4-, PO432) Mass action expressions:
[ H ][OH ]
Kw
10 14
[ H 2O ]
K A, 2 10 7.0
[ H ][ HPO42 ]
[ H 2 PO4 ]
[
H
][
H
PO
2.1
2
4 ]
K A,1 10
[ H 3 PO40 ]
K A,3 10 12.2
[ H ][ PO43 ]
[ HPO42 ]
80
3) Mass balance:
PT = [H3PO40] + [H2PO4-] + [HPO42-] + [PO43-]
4) Charge balance:
[H+] = [OH-] + [H2PO4-] + 2[HPO42-] + 3[PO43-]
Assumptions: Because phosphoric acid is an
acid, assume that [H+] >> [OH-]. Also, because
KA,2 and KA,3 are quite small, then [HPO42-] and
[PO43-] are negligible compared to [H3PO40] and
[H2PO4-]. The mass balance then becomes:
PT = [H3PO40] + [H2PO4-]
81
KA,1PT-KA,1[H+] = [H+]2
[H+]2 + KA,1[H+] - KA,1PT = 0
2
K
A
A 4 K A PT
[H ]
2
82
2
-4
[
H
][
HPO
4 ] M
[HK
x
10
3PO ] = 1.014
A, 2
[ H 2 PO4 ]
0 7.0
4
10
[ HPO42 ]
[ H 2 PO4 ]K A, 2
[H ]
K A, 2 10 7.0 M
83
K A,3 10 12.2
[ H ][ PO43 ]
[ HPO42 ]
K A,3 10 12.2
10 3.05 [ PO43 ]
10 7.0
84
CALCULATION OF pH OF A
VOLATILE BASE
Compute the pH and concentrations of all
species of a solution exposed to an
atmosphere of pNH3 = 10-4 atm.
1) Species: NH30, NH4+, OH-, H+
2) Mass action expressions:
0
[
NH
[ H ][OH ]
1.75
14
3]
K H 10
Kw
10
p NH
[ H 2O ]
3
K B 104.5
[ NH 4 ][OH ]
[ NH 30 ][ H 2O ]
85
[ NH 4 ][OH ] [OH ]2
0
[ NH 3 ]
10 2.25
[OH-]2 = 10-6.75
[OH-] = 10-3.375 M = 4.22 x 10-4 M
86
GRAPHICAL APPROACH TO
EQUILIBRIUM CALCULATIONS
Consider the monoprotic acid HA:
[
H
][
A
]
5.5
K A 10
[ HA0 ]
CT = 10-3 = [HA0] + [A-]; so [A-] = CT [HA0]
KA[HA0] = [H+][A-]
KA[HA0] = [H+](CT - [HA0])
KA[HA0] = [H+]CT - [H+][HA0]
C
[
H
] [H+]C
0 +
T 0] =
KA[HA0] [+
[H
][HA
HA ]
T
K A [H ]
88
[ H ][ A ]
KA
CT [ A ]
CTKA - KA[A-] = [H+][A-]
CTKA = [A-]([H+] + KA)
CT K A
[A ]
[H ] K A
1) At pH < pKA, [H+] >> KA so [H+] + KA
[H+]
[HA0] = CT([H+]/[H+]) = CT
log [HA0] = log CT
[A-] = CTKA/[H+]
log [A-] = log CT - pKA + pH
89
90
A-
HA
log [i]
-4
10-3 M HA
OH10-3 M NaAc
-6
-8
+
H
-10
0
10
12
14
pH
91
[H 2S ]
K1
K1 K 2
1 2
[H ] [H ]
[ HS ]
[H ]
K2
1
K1
[H ]
ST
[S ]
[ H ]2 [ H ]
1
K1 K 2
K2
2
93
[H 2S ]
ST
K1
K1 K 2
1 2
[H ] [H ]
ST
ST
[ HS ]
[H ]
K2
[H ]
1
K1
[H ]
K1
ST
ST
ST
[S ]
[H ] [H ]
[ H ]2
1
K1 K 2
K2
K1 K 2
2
94
ST
[H 2S ]
K1
K1 K 2
2
1 2
[H ] [H ]
0
[ HS ]
ST
ST
[H ]
K2
1
K1
[H ]
ST
ST
ST
[S ]
[H ] [H ]
2[ H ]
1
K1 K 2
K2
K2
2
95
ST
ST
[H 2S ]
K1
K1 K 2
K1
1 2
[H ] [H ]
[H ]
ST
[ HS ]
[H ]
K2
1
K1
[H ]
ST
ST
ST
[S ]
[H ] [H ]
[H ]
1
K1 K 2
K2
K2
2
96
ST
ST
[H 2S ]
K1
K1 K 2
2 K1
1 2
[H ] [H ]
[H ]
ST
[ HS ]
[H ]
K2
1
K1
[H ]
ST
ST
ST
[S ]
[H ] [H ]
2
1
K1 K 2
K2
97
ST
[H 2S ]
K1
K1 K 2
K1 K 2
1 2
[H ] [H ]
[ H ]2
0
ST
ST
ST
[ HS ]
K2
[H ]
K2
1
[
H
]
K1
[H ]
ST
[S ]
ST
2
[H ] [H ]
1
K1 K 2
K2
98
H2S
HS
-4
2-
lo g [i]
-6
-8
OH-
-10
-12
0
pH
10
12
14
99
IONIZATION FRACTIONS
Monoprotic acid: HB
B = 1 [B]/C = KA/(KA + [H+])
HB = 0 [HB]/C = [H+]/(KA + [H+])
1 + 0 = 1
Diprotic acid: H2A
[ H 2 A]
1
0
K1
K1 K 2
C
1 2
[H ] [H ]
100
[ HA ]
1
1
[H ]
K2
C
1
K1
[H ]
[ A2 ]
1
2
[ H ]2 [ H ]
C
1
K1 K 2
K2
0 1 2 1
101
102
Chemical equations
Combine equations
Making Simplifying
Assumptions
If CHCl is large enough that [OH-] [Cl-]
Then charge balance becomes [H+] = [Cl-]
It works for 0.10 M HCl
It doesnt work for 1.0 x 10-8 M HCl
Making assumption leads to pH 8.00 solution
A basic solution of HCl? Impossible!
(mass balance)
(charge balance)
Solving It Exactly
Combine Ka and mass balance, solve for
[A-]
[H+][A-]/Ka + [A-] = CHA
[A-] = CHAKa/([H+] + Ka)
For 0.10 M HA
x3 + 1.8 x 10-5x2 1.8 x 10-6x 1.8 x 10-19 = 0
x = 1.33 x 10-3 (pH 2.88)
Making Simplifying
Assumptions
Look what happens if [OH-] [A-] in
charge balance
You did this automatically in Chem 106
by saying [H+] = [A-] = x
More Assumptions
Now, if [H+] CHA (5% rule)
The quadratic on previous slide becomes
Mass balances
[Na+] = CNaA
[HA] + [A-] = CNaA
Charge balance
[Na+] + [H+] = [A-] + [OH-]
Mass balances
[Na+] = CNaA
[HA] + [A-] = CHA + CNaA
Charge balance
[Na+] + [H+] = [A-] + [OH-]
Mass balance
[H2A] + [HA-] + [A2-] = CH2A
Solution of MgCl2
Species in solution
H+, OH-, Mg2+, Cl-
Mass balances
[Mg2+] = CMgCl2 and [Cl-] = 2CMgCl2
Charge balance
[H+] + 2[Mg2+] = [OH-] + [Cl-]
Neglecting H+ and OH-, we have
2[Mg2+] = [Cl-] Is that right?
Mass balance
[Cd2+] = [S2-] + [HS-] + [H2S]
Charge balance
2[Cd2+] + [H+] = 2[S2-] + [HS-] + [OH-]
Polyprotic Acids
Interesting Features of
plots
First, notice that the pH where two
species concentrations are the same
is around the pKa for that
equilibrium. In fact, for polyprotic
acids with pKa's that differ by over 3
to 4 units, the pH is equal to the pKa.
pKa1
pKa2 pKa3
H
R
C COOH
neutral
C COOH
NH3
NH2
amino-protonated
H
R
C COO
NH3
H
R
C COO
NH2
zwitterion
carboxylic-deprotonated
Both groups protonated
C COOH
K1
H
H
NH3
C COO
K2
H
H
NH3
H2Gly+
NH2
Gly-
HGly
glycinate
glycinium
K 1 10
C COO
2.35
[ H ][ HGly ]
[ H 2 Gly ]
K 2 10
9.78
[ H ][Gly ]
[ HGly ]
[ H ][ HGly ]
K [ HGly ] K w
[H ] 2
K1
[H ]
[H ]
[H ]
K 2 [ HGly ] K w
[ HGly ] / K 1 1
HGly
H2Gly+
Gly-
high pH
low pH
Carboxyl group
Loses H+
ammonium group
Loses H+
Equilibrium reactions
Diprotic acid:
K a1 K1
K a2 K 2
Equilibrium reactions
K b1
Diprotic base:
K b2
Relationship between Ka and Kb
K a1 K b 2 Kw
K a 2 K b1 Kw
pKa of carboxy
and ammonium
group vary
depending on
substituents
Largest
variatio
ns
high pH
low pH
Carboxyl group
Loses H+
ammonium group
Loses H+
K1=4.70x10-3
K2=1.80x10-10
K1 K 2
Assume H2L+ behaves as a monoprotic acid
K a K1
+ H+
H2L+
HL
H+
0.0500 - x
[HL][H ]
x2
x 1.32 x10 2 M [ HL ] [ H ]
Fx
[H 2 L ]
[L ]
1.80 10 -10 ( K a 2 )
[ L ] 1.80 10 10 1.32 10 2 [ HL ]
Validates assumption
K b1 Kw / K a 2 5.55 10 5
K b2 Kw / K a 2 2.13 10 12
K b1 K b2
K b K b1
L-
HL
0.0500 - x
OHx
[HL][OH - ]
[L- ]
x2
x 1.64 x10 3 M [ HL ] [ OH ]
Fx
Kw
1 10
[ OH ]
14
1.64 10
6.10 10 12 M pH 11 .21
Determine [L-]:
[ L ] F x 4.84 10 2 M
[H 2 L ]
[HL]
x
[ H 2 L ] 2.13 10 12 1.64 10 3 [ HL ]
Validates assumption [OH-] [HL],
K a K a 2 1.80 10 10
K b K b2 2.13 10 12
Step 1:
Step 2:
K1
K b2
K2
K b1
Charge Balance:
[H ] [H 2 L ] [L- ] [OH - ]
Step 3:
Mass Balance:
Step 4:
F [ HL] [ H 2 L ] [ L- ]
[HL][H ]
[L ][H ]
[H 2 L ][OH ] K
K1
b2
K2
K
b1
[HL]
[HL]
[H 2 L ]
[HL][OH - ]
[L ]
Step 6: Solve:
Substitute Acid Equilibrium Equations into charge
balance:
[
HL
][
H
] [L- ] [HL]K 2 [OH - ] Kw
[H2 L ]
[H 2 L ] [L ] [H ] [OH ] 0
[H ]
K1
[H ]
[HL][H ] [HL]K 2
Kw
[
H
]
K1
[H ]
[H ]
Multiply by
[H+]
[HL][H ]2
[HL]K 2 [H ]2 Kw 0
K1
Step 6: Solve:
[HL][H ]2
[HL]K 2 [H ]2 Kw 0
K1
Factor out
[H+]2:
[HL]
1 K 2 [HL] Kw
K1
[H ]2
Rearrange
:
[H ] 2
K 2 [HL] Kw
[HL]
1
K1
Step 6: Solve:
[H ] 2
K 2 [HL] Kw
[HL]
1
K1
[H ]
K 2 K1 [HL] K1Kw
K1 [HL]
[H ]
K 2 K1F K1Kw
K1 F
Step 6: Solve:
[H ]
K 2 K1F K1Kw
K1 F
Calculate a
pH:
[H ]
9.36 x10 6
K1
4.70 x10 3
[L ]
[HL]K 2
[H ]
1.02 x10 5
Valid
[HL]=0.0500M >> 9.36x10-6 [H2L+] & 1.02x10-5 [L-Assumption
]
Summary of results:
pH
[H+] (M)
[H2L+] (M)
[HL] (M)
[L-] (M)
Acid form
0.0500 M H2A
1.88
1.32x10-2
3.68x10-2
1.32x10-2
1.80x10-10
Intermediate form
0.0500 M HA-
6.06
8.80x10-7
9.36x10-6
5.00x10-2
1.02x10-5
Basic form
0.0500 M HA2-
11.21
6.08x10-12
2.13x10-12
1.64x10-3
4.84x10-2
[H ]
K 2 K1F K1Kw
K1 F
[H ]
K 2 K1F
K1 F
Assume K1<< F:
[H ]
K 2 K1F
F
[H ]
K 2 K1F
F
Cancel F:
[H ] K 2 K1
Take the -log:
Independent of
concentration:
1
2
pH ( pK1 pK 2 )
pH of intermediate form of a
diprotic acid is close to
midway between pK1 and
pK
Diprotic Systems
Follows same process as monoprotic systems
[H 2 A]
[H ]2
H2 A
2
F
[H ] [H ]K1 K1K 2
K1 [H ]
[HA ]
HA
2
F
[H ] [H ]K1 K1K 2
Fraction in the form A2-:
A2
[ A2 ]
K1K 2
2
F
[H ] [H ]K1 K1K 2
Neutral zwitterion
Only ions are H2A+, A-, H+ and OHConcentrations are not equal to each other
Isoionic point: [H ]
K1K 2 F K1Kw
K1 F
pH obtained by simply
dissolving alanine
[HA][H ]
[H2 A ]
K1
[ A- ]
K 2 [HA]
[H ]
[HA][H ] K 2 [HA]
[
H
] K1 K 2
K1
[H ]
Solution:
For isoionic point:
[H ]
K1K 2 F K1Kw
K1 F
7.7 10 7 M pH 6.11
10 2.34 0.10
Solution:
For isoelectric point:
1