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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 Acid-Base 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 10-12 M [K+] = 0.0550 M
[OH-] = 0.0020 M
[H2PO4-] = 1.3 x 10-6 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 material-balance)


Equations
The mass-balance 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 9-11

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 = 3.910-11

F-+H2O HF + OH-

[HF][OH ]
11
Kb

1
.
5

10
[F ]

H2O H+ + OH-

Kw = [H+][OH-] = 1.010-14

(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 = 3.910-11

[HF][OH ]
11
Kb

1
.
5

10
[F ]
Kw = [H+][OH-] = 1.010-14

(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-] = 1.010-14

2[Ca2+] = [F-] + [HF]


Ksp = [Ca2+][F-]2 = 3.910-11

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+] = 1.010-3 M
Kw

[OH-] = 1.010-11 M

Kb
[HF-] =1.5[F-]
Mass
[Ca2+] = 3.910-4 M

[F-] =0.80[Ca2+]
Ksp

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 10-11) and Ka (7 x 10-4) 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 = (4x10-11 / 4)1/2(1+10-3/7x10-4) = 7.7x10-6


[Ca2+] = 4x10-4 M (This is the solubility s)
If no Ka

4x10-11 = s (2s)2

s = 2x10-4

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-] = 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

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 10-3 M Benzoic


Acid

System with 10-3 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-] = 10-14
HA = H+ + AKA = [H+][A-]/[HA] = 10-pKa
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-] = 10-14
HA = H+ + AKA = [H+][A-]/[HA] = 10-pKa
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-] = 10-14
H2B = H+ + HBKA1 = [H+][HB-]/[H2B] = 10-pKa1
HB- = H+ + B2KA2 = [H+][B2-]/[HB-] = 10-pKa2
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-] = 10-14
H2B = H+ + HB- KA1 = [H+][HB-]/[H2B] = 10-pKa1
HB- = H+ + B2- KA2 = [H+][B2-]/[HB-] = 10-pKa2
Mass Balance: BT = [H2B] + [HB-] +[B2-]= 10-3 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-] = 10-14
H2B = H+ + HB- KA1 = [H+][HB-]/[H2B] = 10-pKa1
HB- = H+ + B2- KA2 = [H+][B2-]/[HB-] = 10-pKa2
Mass Balance: BT = [H2B] + [HB-] +[B2-]= 10-3 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 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

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 10-4 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 + (7x10-10)[H+]2 - (3.6x10-13)[H+] - (7x10-24) =

We can solve this by trial and error, computer or

graphical methods. From trial and error we obtain


[H+] = 6.1x10-7 M or pH = 6.21

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

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 10-7
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 10-4 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 10-15


[H+] = 5.92 x 10-7 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 10-4
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 10-4 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 10-4) = 3.70, and [Cl-] =
2 x 10-4 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 10-4.5 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-] = 10-4.5


M=C
[Na+] = 10-4.5 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-] 10-4.5 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+] = (10-4.710-14/(10-4.5 + 10-4.70)
[H+] = 6.2 x 10-8 M
pH = 7.2
pOH = pKw - pH = 14.0 - 7.2 = 6.8
[OH-] = 1.61 x 10-7
73

Rearranging the proton condition we get:


[HAc0] = [OH-] - [H+] = 1.6 x 10-7 - 6.2 x
10-8
= 9.8 x 10-8
Check of assumption:
[Ac-] = C - [HAc0] = 10-4.50 - 9.8 x 10-8
so [Ac-] 10-4.50
and the assumption made is valid.

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 ]

3) Mass balance expressions:


PT = 10-3.7 M = [H2P0] + [HP-] + [P2-]
75

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

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 10-5


pH = 4.62

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

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,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

[H+] = 8.986 x 10-4 M


pH = 3.05
pOH = pKw - pH = 14 - 3.05 = 10.95
[OH-] = 1.122 x 10-11 M
[H3PO40] = PT - [H2PO4-] = 10-3 - 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-] = 10-16.15 M = 7.079 x 10-17 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 = 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

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 = 10-4(101.75) = 10-2.25 M
K B 10 4.5

[ 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

pH = pKw - pOH = 14 - 3.375 =


10.625
so the assumption that [OH-] >>
[H+] is valid.
The concentrations are then:
[OH-] = 4.22 x 10-4 M
[NH4+] = 4.22 x 10-4 M
[H+] = 2.37 x 10-11 M
[NH30] = 5.62 x 10-3 M
87

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

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

10-3 M HA

OH10-3 M NaAc

-6

-8
+

H
-10
0

10

12

14

pH
91

To compute the composition of a 10-3 M


solution of HA, we start with the
charge balance:
[H+] = [A-] + [OH-]
[H+] >> [OH-]
[H+] [A-]
To compute composition of 10-3 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 = 10-3 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 = 10-3 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 3.10a-c 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 10-8 M HCl


We get [H+] = 0.10 M (pH 1.00) and 1.05 x 10-7 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 10-8 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 10-8 M HA
Given Ka = 1.8 x 10-5
Compare with strong acid

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)

For 1.0 x 10-8 M HA


x3 + 1.8 x 10-5x2 1.9 x 10-13x 1.8 x 10-19 = 0
x = 1.05 x 10-7 (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 10-5 M
One based on total silver-containing species
One based on total nitrogen-containing 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 half-way between the pKa points.
For example, the point where [H2PO4-] is a maximum lies half-way
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

amino-protonated

H
R

C COO
NH3

H
R

C COO
NH2

zwitterion
carboxylic-deprotonated
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 Acid-Base 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 Acid-Base Equilibria


Diprotic Acids and Bases
3.) General Process to Determine pH

Acid Form (H2L+)

Illustration with amino acid leucine

K1=4.70x10-3

K2=1.80x10-10

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 Acid-Base Equilibria


Diprotic Acids and Bases
3.) General Process to Determine pH

0.050 M leucine hydrochloride


K1=4.70x10-3

+ 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 Acid-Base 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 non-zero. 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 Acid-Base 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 Acid-Base 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 Acid-Base 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 non-zero. 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 Acid-Base 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 Acid-Base 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 Acid-Base 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 Acid-Base 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 Acid-Base 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 Acid-Base 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 Acid-Base 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 >> 9.36x10-6 [H2L+] & 1.02x10-5 [L-Assumption
]

Polyprotic Acid-Base 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

1.32x10-2

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

Range of pHs and concentrations for three different forms

Polyprotic Acid-Base 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 Acid-Base 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 Acid-Base 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 Acid-Base 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 Acid-Base 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 Acid-Base 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 Acid-Base 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 Acid-Base 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