Treatment for Multiple
Chemical Equilibrium
MASS BALANCE AND
CHARGE BALANCE
EQUATION
Mass and Charge Balance
Equations
In a solution of electrolytes, the stoichiometry leads to mass or
material balance (mbe) and charge balance equations (cbe).
The merit is to consider the various ion species and equilibria in the
solution when we write these equations.
In a 0.10 M NaHCO3 solution,
mbe: 0.10 = [Na+] = [H2CO3] + [HCO3 ] + [CO32 ]
cbe: [Na+] + [H+] = [HCO3 ] + 2 [CO32 ] + [OH]
Consider these
equilibrium eqn for
mbe and cbe:
NaHCO3 = Na+ +
HCO3HCO3 + H2O = H2CO3 +
OH18 AcidBase Equilibria

2
Charge Balance Equations
The charge balance equation is an
algebraic statement that the sum of all
positive charges in the solution must
equal the sum of all of the negative
charges. In writing charge balance
equations, the coefficient in front of
each species is always the magnitude
of the charge on that ion; example, for
the phosphate ion, 3[PO4].
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.
Charge Balance Equations
Charge Balance Equations An algebraic statement of electroneutrality.
The concentration of the sum of the positive charges =
the concentration of the sum of the negative charges.
General Form of the Equation
n1[C1] + n2[C2] + = m1[A1] + m2[A2] +
n1 and m1 represent the magnitude of the charge of the ion
[C1] and [A1] represent the concentration of each cation and
anion respectively
Charge Balance Examples
Given
[H+] = 5.1 x 1012 M [K+] = 0.0550 M
[OH] = 0.0020 M
[H2PO4] = 1.3 x 106 M
[HPO42] = 0.0220 M [PO43] = 0.0030 M
Find the solution for the Charge
Balance equation.
Charge Balance Examples
Write the charge balance equation
for a solution containing H2O, H+,
OH, ClO4, Fe(CN)63, CN, Fe3+,
Mg2+, CH3OH, HCN, NH3, and NH4+.
Charge Balance Examples
Write a charge balance equation for
aqueous solution of glycine, which
reacts as follows:
+
+
H3NCH2CO2 H2NCH2CO2 + H+
H3NCH2CO2 + H2O +H3NCH2CO2H + OH
Charge Balance Examples
Write a charge balance equation for
a solution of Al(OH)3 dissolved in 1 M
KOH. Possible species are Al3+,
AlOH2+, Al(OH)3, Al(OH)2+, and
Al(OH)4
Mass Balance Equation
Mass Balance (Material Balance) Statement of Conservation of Matter The quantity of all species in a solution
containing a particular atom (or group of
atoms) must be equal to the amount of
that atom (or group of atoms) delivered
to the solution.
Mass Balance Example
(known concentrations)
Write the mass balance equation for
the acetate group of atoms in a 0.05
M solution of acetic acid.
Write the mass balance equation for
the phosphate group of atoms in a
0.025 M solution of phosphoric acid.
Mass Balance Example
(known concentrations)
Write the mass balances for K+ and
for phosphate in a solution prepared
by mixing 0.0250 mol KH2PO4 plus
0.0300 mol KOH and diluting to 1.0 L.
Write a mass balance equation for a
0.05 M solution of glycine in water.
Mass Balance Example
(known concentrations)
Suppose that 0.30 g of AlOOH (FM =
59.99) plus 150 mL of 3.0 M KOH are
diluted to 1.0 L to give the species
Al3+, AlOH2+, Al(OH)3, Al(OH)2+, and
Al(OH)4
Mass Balance Example
(unknown concentrations)
Write the mass balance equation for
La(IO3)3.
Write the mass balance equation for
a saturated solution of slightly
soluble Ag3PO4, which produces PO43and 3Ag+ when it dissolves.
Mass Balance (or materialbalance)
Equations
The massbalance equation is statement of the
conversation of matter. For example in considering a
0.050 M solution of acetic acid
CH3CO2H which dissociates
CH3CO2H(aq) < == > CH3CO2 (aq) + H+(aq)
0.050 M = [CH3CO2H] + [CH3CO2]
If there are several products as in the ionization of a
polyprotic acid, the mass balance must include all
possible species.
Mass balance for the solubility of magnesium
hydroxide (see page 153)
Approach 1: using magnesium as our reference
Step 1: because the starting material is Mg(OH) 2,the amount of
magnesium ions (denoted by X) we have in the solution should be
half of the hydroxide released by Mg(OH)2 (denoted by Y). i.e. X =
Y
Note that the total amount of hydroxide (denoted by Z) in
solution include the hydroxide (Y) from Mg(OH)2 and from the
hydroxide water that is equal to the concentration of [H +] from
water, i.e. Z = Y + [H+]; thus
Y = Z [H+]
Step 2: X exists in water in the forms: [Mg2+], [MgOH+], therefore
X = [Mg2+] + [MgOH+],
hydroxide Z exists in the forms [OH] and [MgOH+],
therefore
Z = [OH] + [MgOH+], thus Y = [OH] + [MgOH+]  [H+];
Step 3: given that X = Y
[Mg2+] + [MgOH+] = ([OH] + [MgOH+]  [H+]);
2( [Mg2+] + [MgOH+]) = [OH] + [MgOH+]  [H+];
2( [Mg2+] + [MgOH+]) + [H+] = [OH] + [MgOH+];
(this is the same as textbook)
Approach 2: Using hydroxide as our
reference
Hydroxide (denoted by X) in solution comes from two sources: (1)
Y amount from Mg(OH)2, which is equal to TWICE amount of
magnesium ions (denoted by M here) Y = 2 M; and source (2) Z
amount from water, that equals the amount of [H+] from water,
i.e. Z = [H+]
We now know X = Y + Z, i.e. X = Y + [H+], i.e. X = 2 M + [H+];
M in solution exists in the forms [Mg2+], [MgOH+],
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]
Mass balance equation for 911
Using calcium as our reference
The amount of calcium (denoted by X) should be equal to the
amount of oxalate (denoted by Y), given that they come from the
same source with a 1:1 stoichoimetric relationship.
X in the system exists as [Ca2+], i.e. X = [Ca2+]
Y in the system exists as [C2O42], [HC2O4], and [H2C2O4],
i.e. Y = [C2O42] + [HC2O4] + [H2C2O4],
Since X = Y, we have [Ca2+] = [C2O42] + [HC2O4] + [H2C2O4] (Final
answer)
Using oxalate as our reference yeilds the same result as above
How about using hydroxide ion as the reference of mass
balance?
Hydroxide ion (denoted by X) in solution comes from water,
which leads
to the formation of [HC2O4] + [H2C2O4],
therefore [OH] = [HC2O4] + [H2C2O4],
MULTIPLE CHEMICAL
EQUILIBRIUM
Equilibrium Calculations
Previous
BaC2O4 Ba2+ + C2O42[Ba2+] = [C2O42]
But what if oxalate then reacted with H2O
C2O42 + H2O HC2O4 + OHHC2O4 + H2O H2C2O4 + OH[Ba2+] [C2O42]
because [C2O42] = [C2O42] + [HC2O4] + [H2C2O4]
Systematic Treatment of Equilibrium
Step 1. Write all pertinent reactions
Step 2. Write the charge balance equation
Step 3. Write the mass balance equation
Step 4. Write the equilibrium constant for each chemical
reaction (should use activities but we will ignore them)
Step 5. Count the equations and unknowns (# equations =
# unknowns)
Step 6. Solve the unknowns
Systematic Treatment of Equilibrium
Determining the equations used to
calculate unknown concentrations is
the heart of this type of problem
The hard part, however, is solving for
multiple unknowns using these
equations
Systematic Treatment of Equilibrium
Calculate the concentration of the
hydronium and hydroxide ions in
water.
Calculate the concentration of Hg22+
in a saturated solution of Hg2Cl2.
Find the solubility of CaF2 in water if
the pH is somehow fixed at 3.0.
Systematic Treatment of Equilibrium
Find the solubility of Ba(C2O4) in
water assuming a pH of 2.0.
Calculate the concentration of all
species in solution.
Systematic Treatment of Equilibrium
We can look for two more pieces of
info:
Charge Balance: Electroneutrality of the
solution; the sum of the positive charge in
[H+] +
2[Ca2+] the
= [OH
] + [Fof
] negative
(4)
solution
equals
sum
charges
in the solution.
Mass Balance: Conservation of matter; the
quantity of
all species
in a solution
2+
2[Ca ] = [F ] + [HF]
(5)
containing a particular atom (or group of
atoms) must equal to the amount of that
atom (or group) delivered to the solution.
27
Systematic Treatment of
Equilibrium
How does the solubility of CaF2 depend on pH?
CaF2(s) Ca2+ + 2F
Ksp = [Ca2+][F]2 = 3.91011
F+H2O HF + OH
[HF][OH ]
11
Kb
1
.
5
10
[F ]
H2O H+ + OH
Kw = [H+][OH] = 1.01014
(1)
(2)
(3)
Five unknowns: [Ca2+], [F], [HF], [H+], and [OH]
Three equations mean we need more equations
28
Systematic Treatment of Equilibrium
We can look for two more pieces of
info:
Charge Balance: Electroneutrality of the
solution; the sum of the positive charge in
[H+] +
2[Ca2+] the
= [OH
] + [Fof
] negative
(4)
solution
equals
sum
charges
in the solution.
Mass Balance: Conservation of matter; the
quantity of
all species
in a solution
2+
2[Ca ] = [F ] + [HF]
(5)
containing a particular atom (or group of
atoms) must equal to the amount of that
atom (or group) delivered to the solution.
Ksp = [Ca2+][F]2 = 3.91011
[HF][OH ]
11
Kb
1
.
5
10
[F ]
Kw = [H+][OH] = 1.01014
(1)
(2)
(3)
[H+] + 2[Ca2+] = [OH] + [F]
(4)
2[Ca2+] = [F] + [HF]
(5)
We need to substitute to get things in terms of Ca2+ or H+
Solving the Equations
[HF][OH ]
11
Kb
1
.
5
10
[F ]
Kw = [H+][OH] = 1.01014
2[Ca2+] = [F] + [HF]
Ksp = [Ca2+][F]2 = 3.91011
Combine eq. 2 and eq. 5, we have
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
]
Its much simpler if
we can consider the
pH fixed (how would
we do that?)
If we can fix pH
pH = 3.00
[H+] = 1.0103 M
Kw
[OH] = 1.01011 M
Kb
[HF] =1.5[F]
Mass
[Ca2+] = 3.9104 M
[F] =0.80[Ca2+]
Ksp
Calculate the Concentration of Ca2+ in a solution that is saturated
in CaF(s) and buffered to pH 3.0.
Write relevant solubility and acid dissociation reactions (how many different ions?)
CaF2(s) Ca2+ + 2FHF H+
F
Write the Ksp (4 x 1011) and Ka (7 x 104) expressions
Ksp = [Ca2+] [F]2
Ka = ([H+] [F]) / [HF]
Write the mass balance equation for Calcium
[Ca2+] = ([F] + [HF])
Calculate the Concentration of Ca2+ in a solution that is saturated
in CaF(s) and buffered to pH 3.0.
[Ca2+] = ([F] + [HF])
Use the Ka expression to substitute for HF and then the Ksp expression to substitute for F 
[Ca2+] = ([F] + ([H+][F])/ Ka) = [F](1 + [H+]/Ka)
[Ca2+] = (Ksp/[Ca2+])1/2 (1 + [H+]/Ka)
[Ca2+]1.5 = (Ksp/4)1/2 (1 + [H+]/Ka)
Solve for [Ca2+]; how does this differ from value if HF were strong acid?
[Ca2+]1.5 = (4x1011 / 4)1/2(1+103/7x104) = 7.7x106
[Ca2+] = 4x104 M (This is the solubility s)
If no Ka
4x1011 = s (2s)2
s = 2x104
Lecture 10 Proton Balance, Graphical
Solutions & Ionization Fractions for
Multiprotic Systems
Proton balance equation (mass balance
on H+)
Graphical solutions for multiprotic
systems
Plot species concentration (pC) versus
Master Variable (pH)
Diprotic
[H+]: pH = pH
[OH]: pOH = pKW  pH
[H2B] = BT* 0
[HB] = BT* 1
[B2] = BT* 2
Start with System Definition
System: Closed
Components: HA & H2O
Species: HA, A, H2O, OH, H+
Equilibria: H2O = H+ + OH
Kw = [H+][OH] = 1014
HA = H+ + AKA = [H+][A]/[HA] = 106
Mass Balance: AT = [HA] + [A] = 103 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
Lines for the acid species
Acid species [HA]: Combine mass balance and
mass action to get
H A
[ HA]
K H
In log form
log[ HA] log H log A log K H
T
At low pH (pH << pKA)
log[ HA] log AT
At high pH (pH >> pKA)
log[ HA] log H log AT log K A
pH dependence of pHA
HA
Lines for the acid species
Conjugate base [A]: Combine mass balance and
mass action to get
K A AT
[A ]
KA H
In log form
log[ A ] log K A log AT log K A H
At low pH (pH << pKA)
log[ A ] log K A log AT log H
At high pH (pH >> pKA)
log[ A ] log AT
Including dependence of [A]
with pH
Complete system
Intercep
t ~ 0.3
log
below AT
System with 103 M Benzoic
Acid
System with 103 M Benzoic
Acid
What is the equilibrium pH for a
solution comprised of AT M of the salt
of the
conjugate base, NaA?
System:
Closed
Components: Na+, HA & H2O
Species: HA, A, H2O, OH, H+
Equilibria: H2O = H+ + OHKw = [H+][OH] = 1014
HA = H+ + AKA = [H+][A]/[HA] = 10pKa
Mass Balance: AT = [HA] + [A]
NaT = [Na+] = AT
Charge Balance: [A] + [OH] = [H+] + [Na+]
Proton Balance equation: [HA] + [H +] = [OH]
Monoprotic Weak Acid  NaAcetate
(salt of the conjugate base)
What is the equilibrium pH for a
solution comprised of AT M of the salt
of the
conjugate base, NaA?
System:
Closed
Components: Na+, HA & H2O
Species: HA, A, H2O, OH, H+
Equilibria: H2O = H+ + OHKw = [H+][OH] = 1014
HA = H+ + AKA = [H+][A]/[HA] = 10pKa
Mass Balance: AT = [HA] + [A]
NaT = [Na+] = AT
Charge Balance: [A] + [OH] = [H+] + [Na+]
Proton Balance equation: [HA] + [H +] = [OH]
Monoprotic Weak Acid  NaAcetate
(salt of the conjugate base)
Monoprotic Weak Acid  NaCN (salt
of the conjugate base)
What is the equilibrium pH for a
solution comprised of BT M of a generic
acid diprotic acid H2B?
System: Closed
Components: H2B & H2O
Species: H2B, HB,B2 H2O, OH, H+
Equilibria: H2O = H+ + OHKw = [H+][OH] = 1014
H2B = H+ + HBKA1 = [H+][HB]/[H2B] = 10pKa1
HB = H+ + B2KA2 = [H+][B2]/[HB] = 10pKa2
Mass Balance: BT = [H2B] + [HB] +[B2]
Charge Balance ( = PBC): 2[B2] + [HB] + [OH] = [H+]
Diprotic Acid  Carbonate
system
System
points
CT
What is the equilibrium pH for a
solution comprised of BT M of the salt
of the
conjugate base of H2B?
System:
Closed
Components: Na+, H2B & H2O
Species: H2B, HB,B2 H2O, OH, H+
Equilibria:
H2O = H+ + OHKw = [H+][OH] = 1014
H2B = H+ + HB KA1 = [H+][HB]/[H2B] = 10pKa1
HB = H+ + B2 KA2 = [H+][B2]/[HB] = 10pKa2
Mass Balance: BT = [H2B] + [HB] +[B2]= 103 M
NaT = [Na+] = BT
Charge Balance: 2[B2] + [HB] + [OH] = [H+] + [Na+]
Proton Balance: [H2B] + [H+] = [B2] + [OH]
Diprotic Acid  NaHCO3 (salt of the
conjugate base of H2B)
What is the equilibrium pH for a
solution comprised of BT M of the salt
of the
conjugate base of HB?
System:
Closed
Components: Na+, HB & H2O
Species: H2B, HB,B2 H2O, OH, H+
Equilibria:
H2O = H+ + OHKw = [H+][OH] = 1014
H2B = H+ + HB KA1 = [H+][HB]/[H2B] = 10pKa1
HB = H+ + B2 KA2 = [H+][B2]/[HB] = 10pKa2
Mass Balance: BT = [H2B] + [HB] +[B2]= 103 M
NaT = [Na+] = 2BT
Charge Balance: 2[B2] + [HB] + [OH] = [H+] + [Na+]
Proton Balance: 2[H2B] + [HB] + [H+] = [OH]
Diprotic Acid  NaHCO3 (salt of the
conjugate base of HB)
NUMERICAL EQUILIBRIUM
CALCULATIONS
Monoprotic acid
What are the pH and the
concentrations of all aqueous
species in a 5 x 104 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
2) Write the reactions and find the
equilibrium constants relating
concentrations of all species:
H2O H+ + OH[ H ][OH ]
14
(i)
Kw
10
[ H 2O]
B(OH)30 + H2O B(OH)4 + H+
[ H ][ B (OH ) ]
10
(ii)
KA
7
x
10
[ B (OH ) 30 ][ H 2O]
59
3) Write down all mass balance
relationships:
5 x 104 M = B
= [B(OH)4] + [B(OH)30] (iii)
4) Write down a single chargebalance (electroneutrality)
expressions:
[H+] = [B(OH)4] + [OH] (iv)
5) Solve n equations in n unknowns.
60
EXACT NUMERICAL SOLUTION
Eliminate [OH] in (i) and (iv)
[H+][OH] = Kw
[OH] = Kw/[H+]
[H+] = [B(OH)4] + Kw/[H+]
[H+]  [B(OH)4] = Kw/[H+]
Kw
[H ]
[ H ] [ B (OH ) 4 ]
(v)
61
Solve (iii) for [B(OH)30]
[B(OH)30] = B  [B(OH)4]
[ H ][ B (OH ) ]
KA
B [ B (OH ) ]
[H+][B(OH)4] = KA(B  [B(OH)4])
(vi)
Now solve (v) for [B(OH)4]
 [B(OH)4] = Kw/[H+]  [H+]
[B(OH)4] = [H+]  Kw/[H+]
62
[H+]([H+]  Kw/[H+]) = KA(B  [H+] + Kw/[H+])
[H+]2  Kw = KAB  KA[H+] + KAKw/[H+]
[H+]3  Kw[H+] = KAB[H+]  KA[H+]2 + KAKw
[H+]3 + KA[H+]2  (KAB + Kw)[H+]  KAKw = 0
H+]3 + (7x1010)[H+]2  (3.6x1013)[H+]  (7x1024) =
We can solve this by trial and error, computer or
graphical methods. From trial and error we obtain
[H+] = 6.1x107 M or pH = 6.21
63
[OH] = Kw/[H+]
[OH] = 1014/106.21
[OH] = 107.79 M
[B(OH)4] = [H+]  Kw/[H+]
[B(OH)4] = 6.1x107  1.62x108
[B(OH)4] = 5.94x107 M
[B(OH)30] = B  [B(OH)4]
[B(OH)30] = 5x104  5.94x107 M = 4.99x104 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 = KABKA[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
In our case this becomes:
2
K
A
A 4 K A B
[H ]
2
Only the positive root has any physical meaning.
[H+] = 5.92 x 107
We could have made this problem even simpler.
Because boric as is a quite weak acid (i.e., very
KA value, very little of it will be ionized, thus
[B(OH)30] >> [B(OH)4]
B [B(OH)30] = 5 x 104 M
67
[ 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+]2 = 3.5 x 1015
[H+] = 5.92 x 107 M
s wise to check your assumptions by back substituti
to original equations. If the error is 5%, the approx
ation is probably justified because KA values are at le
this uncertain!
68
CALULATE THE pH OF A STRONG
ACID
Compute the pH and equilibrium
concentrations of all species in a 2 x 104
M solution of HCl.
1) Species: H+, Cl, HCl0, OH2) Mass action laws:
[ H ][OH ]
[
H
][
Cl
]
14
3
Kw
10
KA
10
[ H 2O ]
[ HCl 0 ]
3) Mass balance: [HCl0] + [Cl] = 2 x 104 M
4) Charge balance: [H+] = [Cl] + [OH]
69
Assumptions: HCl is a very strong acid so
[H+] >> [OH] and [Cl] >> [HCl0]
Now the only source of H+ and Cl are the
dissociation of HCl, so
[H+] = [Cl]
(this is also apparent from the charge
balance)
Thus, pH =  log (2 x 104) = 3.70, and [Cl] =
2 x 104 M.
+
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
CALCULATE THE pH OF A WEAK
MONOPROTIC BASE
Compute the pH and equilibrium concentrations of
all species in a 104.5 M solution of sodium acetate.
1) Species: H+, Na+, Ac, HAc0, OH2) Mass action laws:
[ H ][ Ac ]
4.70
KA
10
[ HAc 0 ]
[ H ][OH ]
Kw
10 14
[ H 2O]
3) Mass balances: [HAc0] + [Ac] = 104.5
M=C
[Na+] = 104.5 M = C
4) Electroneutrality: [Na+] + [H+] = [Ac] +
[OH]
71
Combine 3) and 4) to get proton
We cannot make any approximations relative to
the concentrations of [H+] and [OH] because
acetate is a weak base and total acetate
concentration is low. However, because base is
weak: [Ac] >> [HAc0] so
[Ac] 104.5 M = C
Substitute for [OH] in proton condition
[HAc0] + [H+] = Kw/[H+]
[HAc0] = Kw/[H+]  [H+]
Now substitute into ionization constant expression
[ H ][ Ac ]
4.70
KA
10
[ HAc 0 ]
[ H ]C
KA
Kw
[
H
]
[H ]
72
[H+]C = KAKw/[H+]  KA[H+]
[H+]2C = KAKw  KA[H+]2
[H+]2C + [H+]2KA = KAKw
[H+]2(C + KA) = KAKw
[H+]2 = KAKw/(C + KA)
[H+] = (KAKw/(C + KA))0.5
[H+] = (104.71014/(104.5 + 104.70)
[H+] = 6.2 x 108 M
pH = 7.2
pOH = pKw  pH = 14.0  7.2 = 6.8
[OH] = 1.61 x 107
73
Rearranging the proton condition we get:
[HAc0] = [OH]  [H+] = 1.6 x 107  6.2 x
108
= 9.8 x 108
Check of assumption:
[Ac] = C  [HAc0] = 104.50  9.8 x 108
so [Ac] 104.50
and the assumption made is valid.
74
CALCULATE THE pH OF AN
AMPHOLYTE
Calculate the pH of a 103.7 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 ]
3) Mass balance expressions:
PT = 103.7 M = [H2P0] + [HP] + [P2]
75
PT = 103.7 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
2 K A, 2 K A,1 PT [ H ] K A,1[ H ] K A, 2 K A,1[ H ]
2
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
[H+] = 2.4 x 105
pH = 4.62
79
CALCULATION OF THE pH OF A
POLYPROTIC ACID
Compute the pH and concentrations of all species
in equilibrium in a 103 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
And the charge balance expression becomes:
[H+] = [H2PO4]
which can be substituted into the expression for K A,1.
2
[
H
]
2.1
K A,1 10
PT [ H ]
KA,1PTKA,1[H+] = [H+]2
[H+]2 + KA,1[H+]  KA,1PT = 0
2
K
A
A 4 K A PT
[H ]
2
82
[H+] = 8.986 x 104 M
pH = 3.05
pOH = pKw  pH = 14  3.05 = 10.95
[OH] = 1.122 x 1011 M
[H3PO40] = PT  [H2PO4] = 103  8.986 x 104
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
[PO43] = 1016.15 M = 7.079 x 1017 M
A check of all the assumptions shows that they are a
valid.
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 = 104 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
3) Charge balance: [NH4+] + [H+] = [OH]
Assumptions: NH3 is a moderate base, so
we can assume that [OH] >> [H+] so
the charge balance becomes
[NH4+] = [OH]
also
[NH30] = pNH3KH = 104(101.75) = 102.25 M
K B 10 4.5
[ NH 4 ][OH ] [OH ]2
0
[ NH 3 ]
10 2.25
[OH]2 = 106.75
[OH] = 103.375 M = 4.22 x 104 M
86
pH = pKw  pOH = 14  3.375 =
10.625
so the assumption that [OH] >>
[H+] is valid.
The concentrations are then:
[OH] = 4.22 x 104 M
[NH4+] = 4.22 x 104 M
[H+] = 2.37 x 1011 M
[NH30] = 5.62 x 103 M
87
GRAPHICAL APPROACH TO
EQUILIBRIUM CALCULATIONS
Consider the monoprotic acid HA:
[
H
][
A
]
5.5
K A 10
[ HA0 ]
CT = 103 = [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
2) pH = pKA; [H+] = KA so [H+] + KA =
2[H+]
[HA0] = CT[H+]/(2[H+]) = CT/2
log [HA0] = log CT  log 2 = log CT  0.301
[A] = CT [H+]/(2[H+]) = CT/2
log [A] = log CT  log 2 = log CT  0.301
3) pH > pKA; [H+] << KA so KA+ [H+] KA
[HA0] = CT[H+]/KA
log [HA0] = log CT + pKA  pH
[A] = CTKA/KA = CT
log [A ] = C

90
peciation diagram for HA with pKA = 5.5 and CT = 10
2
0
A
HA
log [i]
4
103 M HA
OH103 M NaAc
6
8
+
H
10
0
10
12
14
pH
91
To compute the composition of a 103 M
solution of HA, we start with the
charge balance:
[H+] = [A] + [OH]
[H+] >> [OH]
[H+] [A]
To compute composition of 103 M NaA
solution, start with proton condition:
[HA0] + [H+] = [OH]
[OH] >> [H+]
[HA0] [OH]
92
SPECIATION DIAGRAM FOR A
DIPROTIC SYSTEM
Consider H2S with pK1 = 7.0, pK2 =
13.0
0
2S0 T = 103 SM
=
[H
S
]
+
[HS
]
+
[S
ST ]
2
[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
1) pH < pK1 < pK2; [H+] > K1 > K2
[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
log [H2S0] = log ST
log [HS] = log (STK1) + pH
log [S2] = log (STK2K1)
+ 2pH
94
2) pH = pK1 < pK2; [H+] = K1 > K2
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
log [H2S0] = log ST  0.301
log [HS] = log ST  0.301
log [S2] = log (STK2/2)
+ pH
95
3) pK1 < pH < pK2; K1 > [H+] > K2
0
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
log [H2S0] = log (STK1)
 pH
log [HS] = log ST
log [S2] = log (STK2)
+ pH
96
4) pK1 < pK2 = pH; K1 > [H+] = K2
0
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
log [H2S0] = log (STK1/2)
 pH
log [HS] = log ST  0.301
log [S2] = log ST  0.301
97
5) pK1 < pK2 < pH; K1 > K2 > [H+]
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
log [H2S0] = log (STK1K2)
 2pH
log [HS] = log (STK2)  pH
log [S2] = log ST
98
Speciation diagram for H2S with CT = 103 at 25C
2
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
Figure 3.10ac from Stumm and Morgan
102
The Systematic Approach
Write all chemical equations for system
Identify the unknown species
Need as many independent mathematical
equations as unknowns
Equilibrium constant expressions
Mass balance equation(s)
Charge balance equation
Make simplifying assumptions where appropriate
Do the math!
Check assumptions
Strong Monoprotic Acid HCl
Chemical equations
HCl  H+ + Cl and H2O  H+ + OH
Unknown species [H+], [OH], [Cl]
We need three independent equations
[H+][OH] = Kw
(mass balance)
[Cl] = CHCl
[H+] = [OH] + [Cl] (charge balance)
Combine equations
[H+] = Kw/[H+] + CHCl
Rearrange to [H+]2 CHCl[H+] Kw = 0
Solve either one using methods of Lecture 9 or make
simplifying assumptions
Solve for 0.10 M HCl and 1.0 x 108 M HCl
We get [H+] = 0.10 M (pH 1.00) and 1.05 x 107 M (pH 6.98)
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 108 M HCl
Making assumption leads to pH 8.00 solution
A basic solution of HCl? Impossible!
So how do you know when to make
assumptions and when not to?
Thats a good question
Try them and see if answers make sense
Weak Monoprotic Acid HA
Chemical equations
HA  H+ + A and H2O  H+ + OH
Unknown species HA, H+, A, OH We need four independent equations
Kw and Ka expressions
[HA] + [A] = CHA
[H+] = [OH] + [A]
(mass balance)
(charge balance)
Solving It Exactly
Combine Ka and mass balance, solve for
[A]
[H+][A]/Ka + [A] = CHA
[A] = CHAKa/([H+] + Ka)
Put this and [OH] = Kw/ [H+] into charge
balance
[H+] = Kw/ [H+] + CHAKa/([H+] + Ka)
Solve directly by Lecture 9 Excel methods
Or rearrange to cubic equation and use poly on
calculator
Exact Cubic Equation
[H+]3 + Ka[H+]2 (Kw + CHAKa)[H+] KwKa =
0
Solve for 0.10 M HA and 1.0 x 108 M HA
Given Ka = 1.8 x 105
Compare with strong acid
For 0.10 M HA
x3 + 1.8 x 105x2 1.8 x 106x 1.8 x 1019 = 0
x = 1.33 x 103 (pH 2.88)
For 1.0 x 108 M HA
x3 + 1.8 x 105x2 1.9 x 1013x 1.8 x 1019 = 0
x = 1.05 x 107 (pH 6.98)
Now Thats Interesting!
Notice that the pH of 0.10 M HA (weak
acid) is much different than the pH of 0.10
M HCl (strong acid)
pH 2.88 compared to 1.00
But the pH of the very dilute weak acid is
the same as the very dilute strong acid!
Both are pH 6.98
I wonder why that is?
Actually, I know, but do you?
Making Simplifying
Assumptions
Look what happens if [OH] [A] in
charge balance
You did this automatically in Chem 106
by saying [H+] = [A] = x
Charge balance becomes
[H+] = CHAKa/([H+] + Ka) or
[H+]2 + Ka [H+] CHAKa = 0
Just a quadratic
In Chem 106, it was x2/(CHA x) = Ka
More Assumptions
Now, if [H+] CHA (5% rule)
The quadratic on previous slide becomes
[H+]2 + Ka [H+] CHAKa = 0
[H+]2 + ([H+] CHA)Ka = 0
[H+]2 CHAKa = 0
[H+] = CHAKa
Which is what you did in Chem 106 most of the time
Well do more of this sort of thing later
For now, lets just look at more examples
of mass balance and charge balance
equations
NaA, Salt of Weak Acid HA
Species in solution
Na+, A, HA, H+, OH
Mass balances
[Na+] = CNaA
[HA] + [A] = CNaA
Charge balance
[Na+] + [H+] = [A] + [OH]
Plus Kw and Ka for exact solution
Buffer Solution Containing HA and
NaA
Species in solution
Na+, A, HA, H+, OH
Mass balances
[Na+] = CNaA
[HA] + [A] = CHA + CNaA
Charge balance
[Na+] + [H+] = [A] + [OH]
Plus Kw and Ka for exact solution
Weak Diprotic Acid H2A
Species in solution
H+, OH, H2A, HA, and A2
Mass balance
[H2A] + [HA] + [A2] = CH2A
Charge balance (see Example 6.8)
[H+] = 2[A2] + [HA] + [OH]
Is the 2 in the right place? Should it be ?
Plus Kw, Ka1, and Ka2 for exact solution
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?
Plus Kw for exact solution
Slightly Soluble Salt of a Weak Acid
(Example 6.10)
Species in solution
H+, OH, Cd2+, S2, HS, H2S
Mass balance
[Cd2+] = [S2] + [HS] + [H2S]
Charge balance
2[Cd2+] + [H+] = 2[S2] + [HS] + [OH]
Plus Ksp, Kw, Ka1, Ka2 for exact solution
Can you spot the approximations you
made in Chem 106 to do a solubility
problem like this?
Examples 6.7 and 6.11
[Ag(NH3)2]Cl completely dissociates
into Ag(NH3)2+ and Cl Ag(NH3)2+ dissociates in two steps,
with two equilibrium constants
Along with Kw and Kb for NH3, we have
four of the equations we need
There are eight species in solution
We need four more equations
Examples 6.7 and 6.11
Continued
Three mass balances (Example 6.7)
[Cl] = 1.00 x 105 M
One based on total silvercontaining species
One based on total nitrogencontaining species
Note the coefficient of 2 on [Ag(NH3)2+]
Charge balance (Example 6.11)
The last equation in Example 6.7 is not an
independent equation
It can be derived by subtracting the silver mass
balance from the charge balance
Examples 6.12 and 6.13
Additional illustrations of the process
I dont agree with the marginal note
on page 208.
Its true that it is often possible to write
more equations than are necessary
Which means not all of them are
independent
Charge balance is usually pretty easy to
write, so I like to use it rather than try to
find all of the mass balance equations
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.
Take for example the point where [H3PO4]=[H2PO4].
The equilibrium equation relating these two species
is
If we take the log10, or "p", of this equation
Since [H3PO4]=[H2PO4], and log10(1) = 0, pH=pKa1
pKa1
pKa2 pKa3
Second, you might notice that the concentrations of the
conjugate bases are maximum halfway between the pKa points.
For example, the point where [H2PO4] is a maximum lies halfway
between between pKa1 and pKa2. Since H2PO4 is the major species
present in solution, the major equilibrium is the
disproportionation reaction.
This equilibrium cannot be used to solve for pH because [H3O+]
doesn't occur in the equilibrium equation. We solve the pH problem
adding the first two equilibria equations
Note that when we add chemical equilibria, we take the product
of the equilibrium equations. Taking the log10 of the last
equation
Since the disproportionation reaction predicts [H3PO4]=[HPO42]
What about the Z
word??
Zwitterions (German for Double Ion)
a molecule that both accepts and
losses protons at the same time.
EXAMPLES???
How about AMINO ACIDS
H
H
R
C COOH
neutral
C COOH
NH3
NH2
aminoprotonated
H
R
C COO
NH3
H
R
C COO
NH2
zwitterion
carboxylicdeprotonated
Both groups protonated
why activity of proteins are pH
dependent
Lets look at the simplest of the amino acids, glycine
H
H
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 ]
In water the charge balance would be,
[ H 2 Gly ] [ H ] [OH ] [Gly ]
Combining the autoprotolysis of water and the K1 and K2 expressions into the charge balance yields:
[ H ][ HGly ]
K [ HGly ] K w
[H ] 2
K1
[H ]
[H ]
[H ]
K 2 [ HGly ] K w
[ HGly ] / K 1 1
HGly
H2Gly+
Gly
Diprotic Acids and Bases
2.) Multiple Equilibria
Illustration with amino acid leucine (HL)
high pH
low pH
Carboxyl group
Loses H+
ammonium group
Loses H+
Equilibrium reactions
Diprotic acid:
K a1 K1
K a2 K 2
Diprotic Acids and Bases
2.) Multiple Equilibriums
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
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Three components to the process
high pH
low pH
Carboxyl group
Loses H+
Acid Form [H2L+]
Basic Form [L]
Intermediate Form [HL]
ammonium group
Loses H+
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Acid Form (H2L+)
Illustration with amino acid leucine
K1=4.70x103
K2=1.80x1010
H2L+ is a weak acid and HL is a very weak acid
K1 K 2
Assume H2L+ behaves as a monoprotic acid
K a K1
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
0.050 M leucine hydrochloride
K1=4.70x103
+ H+
H2L+
HL
H+
0.0500  x
Determine [H+] from Ka:
K a 4.7 10
[HL][H ]
x2
x 1.32 x10 2 M [ HL ] [ H ]
Fx
[H 2 L ]
Determine pH from [H+]:
pH log[ H ] log( 1.23 10 2 M ) 1.88
Determine [H2L+]:
[ H 2 L ] F x 3.68 10 2 M
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Acid Form (H2L+)
What is the concentration of L in the solution?
[L] is very small, but nonzero. Calculate from Ka2
K [HL]
[H ][L ]
K a2
[L ] a 2
[HL]
[H ]
[L ]
( 1.80 10 10 )( 1.32 10  2 )
( 1.32 10  2 )
1.80 10 10 ( K a 2 )
Approximation [H+] [HL], reduces Ka2 equation to [L]=Ka2
[ L ] 1.80 10 10 1.32 10 2 [ HL ]
Validates assumption
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
For most diprotic acids, K1 >> K2

Even if K1 is just 10x larger than K2

Assumption that diprotic acid behaves as monoprotic is valid
Ka Ka1
Error in pH is only 4% or 0.01 pH units
Basic Form (L)
K b1 Kw / K a 2 5.55 10 5
K b2 Kw / K a 2 2.13 10 12
L is a weak base and HL is an extremely weak base
K b1 K b2
Assume L behaves as a monoprotic base
K b K b1
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
0.050 M leucine salt (sodium leucinate)
L
HL
0.0500  x
OHx
Determine [OH] from Kb:
K b 5.55 10
[HL][OH  ]
[L ]
x2
x 1.64 x10 3 M [ HL ] [ OH ]
Fx
Determine pH and [H+] from Kw:
[H ]
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
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Basic Form (L)
What is the concentration of H2L+ in the solution?
[H2L+] is very small, but nonzero. Calculate from Kb2
[H 2 L ][OH ] [H2 L ]x
K b2
[H 2 L ]
[HL]
x
[ H 2 L ] 2.13 10 12 1.64 10 3 [ HL ]
Validates assumption [OH] [HL],
ully basic form of a diprotic acid can be treated as a monobasic, K b=Kb1
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Intermediate Form (HL)

More complicated HL is both an acid and base
K a K a 2 1.80 10 10
K b K b2 2.13 10 12
Amphiprotic can both donate and accept a proton
Since Ka > Kb, expect solution to be acidic

Can not ignore base equilibrium
Need to use Systematic Treatment of Equilibrium
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Step 1:
Step 2:
Intermediate Form (HL)
Pertinent reactions:
K1
K b2
K2
K b1
Charge Balance:
[H ] [H 2 L ] [L ] [OH  ]
Step 3:
Mass Balance:
Step 4:
Equilibrium constant expression (one for each reaction):
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 ]
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Intermediate Form (HL)
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 ]
All Terms are
related to
[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
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Intermediate Form (HL)
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
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Intermediate Form (HL)
Step 6: Solve:
[H ] 2
K 2 [HL] Kw
[HL]
1
K1
Multiply by K1 and take squareroot:
[H ]
K 2 K1 [HL] K1Kw
K1 [HL]
Assume [HL]=F, minimal
dissociation:
(K1 & K2 are small)
[H ]
K 2 K1F K1Kw
K1 F
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Intermediate Form (HL)
Step 6: Solve:
[H ]
K 2 K1F K1Kw
K1 F
Calculate a
pH:
[H ]
( 4.70 x10 3 )( 1.80 x10 10 )( 0.0500 ) ( 4.70 x10 3 )( 1.0 x10 14 )
4.70 x10 3 0.0500
8.80 x10 7 M pH 6.06
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Intermediate Form (HL)
Step 7: Validate Assumptions
Assume [HL]=F=0.0500M, minimal dissociation (K1 & K2 are
small).
Calculate [L] & [H2L+] from K1 & K2:
[HL][H ] ( 0.0500 )( 8.80 x10 7 )
[H2 L ]
9.36 x10 6
K1
4.70 x10 3
[L ]
[HL]K 2
[H ]
( 0.0500 )( 1.80 x10 10 )
8.80 x10 7
1.02 x10 5
Valid
[HL]=0.0500M >> 9.36x106 [H2L+] & 1.02x105 [LAssumption
]
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Intermediate Form (HL)
Summary of results:
[L] [H2L+] two equilibriums proceed equally even though Ka>Kb
Nearly all leucine remained as HL
Solution
pH
[H+] (M)
[H2L+] (M)
[HL] (M)
[L] (M)
Acid form
0.0500 M H2A
1.88
1.32x102
3.68x102
1.32x102
1.80x1010
Intermediate form
0.0500 M HA
6.06
8.80x107
9.36x106
5.00x102
1.02x105
Basic form
0.0500 M HA2
11.21
6.08x1012
2.13x1012
1.64x103
4.84x102
Range of pHs and concentrations for three different forms
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Simplified Calculation for the Intermediate Form (HL)
[H ]
K 2 K1F K1Kw
K1 F
Assume K2F >>
Kw:
[H ]
K 2 K1F
K1 F
Assume K1<< F:
[H ]
K 2 K1F
F
Polyprotic AcidBase Equilibria
Diprotic Acids and Bases
3.) General Process to Determine pH
Simplified Calculation for the Intermediate Form (HL)
[H ]
K 2 K1F
F
Cancel F:
[H ] K 2 K1
Take the log:
 log [H ] 2 ( log K1 log K 2 )
1
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
Polyprotic AcidBase Equilibria
Polyprotic Acids and Bases
4.) Fractional Composition Equations
Diprotic Systems
Follows same process as monoprotic systems
Fraction in the form H2A:
[H 2 A]
[H ]2
H2 A
2
F
[H ] [H ]K1 K1K 2
Fraction in the form HA:
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
Polyprotic AcidBase Equilibria
Isoelectric and Isoionic pH
1.) Isoionic point is the pH obtained when the pure, neutral
polyprotic acid HA is dissolved in water
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
Remember: Net Charge of Solution is Always
Polyprotic AcidBase Equilibria
Isoelectric and Isoionic pH
2.) Isoelectric point is the pH at which the average charge of the
polyprotic acid is 0
pH at which [H2A+] = [A]

Always some A and H2A+ in equilibrium with HA
Most of molecule is in uncharged HA form
To go from isoionic point (all HA) to isoelectric point, add acid to
decrease [A] and increase [H2A+] until equal

pK1 < pK2 isoionic point is acidic excess [A]
Remember: Net Charge of Solution is Always
Zero!
Polyprotic AcidBase Equilibria
Isoelectric and Isoionic pH
2.) Isoelectric point is the pH at which the average charge of the
polyprotic acid is 0
isoelectric point: [A] = [H2A+]
[HA][H ]
[H2 A ]
K1
[ A ]
K 2 [HA]
[H ]
[HA][H ] K 2 [HA]
[
H
] K1 K 2
K1
[H ]
Isoelectric point: pH 2 ( pK1 pK 2 )
Polyprotic AcidBase Equilibria
Isoelectric and Isoionic pH
3.) Example:
Determine isoelectric and isoionic pH for 0.10 M alanine.
Solution:
For isoionic point:
[H ]
K1K 2 F K1Kw
K1 F
( 10 2.34 )( 10 9.87 )( 0.10 ) ( 10 2.34 )( 1 10 14 )
7.7 10 7 M pH 6.11
10 2.34 0.10
Polyprotic AcidBase Equilibria
Isoelectric and Isoionic pH
3.) Example:
Determine isoelectric and isoionic pH for 0.10 M alanine.
Solution:
For isoelectric point:
1
pH 2 ( pK1 pK 2 ) 2 ( 2.34 9.87 ) 6.10
Isoelectric and isoionic points for polyprotic acid are almost the same
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