7-Acid and Base_S11

1


Acid-Base Reactions and Equilibrium

By Brnsted-Lowry

1) Acid is proton (H
+
) donor or (OH
-
) accepter
- substance which can donate a hydrogen ion (proton), H
+
.

2) Base is proton (H
+
) accepter or (OH
-
) donor
- substance which can accept a hydrogen ion (proton), H
+
.

Note:

By Lewis

1) Acid is an electron pair acceptor
- A Lewis acid is a substance which can accept an electron pair from a Lewise base to form a covalent bond.
2) Base is an electron pair donor

For example, in the formation of an ammonium ion, the proton (H
+
) is the Lewis acid accepting the unshared electron pair on the ammonia.

NH3 + H2O NH4
+
+ OH
-


H H
.. ..
H : N : + H : O :
.. ..
H

Ammonium ion


Lewis base Lewis acid

H + H -
.. ..
H : N : H + : O :
.. ..
H



The structure above is incomplete!


----------------------------
NSEN

Acid-Base and Salts (Deutsch and Whitney, 1972)

- Acids, bases and salts are among the most important of all chemical compounds because they are electrolytes and they dissociate into
ions when dissolved in water.

- Acids, bases, and salts are all electrolytes. Their solutions conduct electricity.

Acids
- An acid is a compound which produces hydronium ion H3O
+
(hydrogen ions H
+
) in water.

- In water, all ions are surrounded by the polar water molecules. Thus it is common to refer to the hydronium ion H3O
+
concentration,
rather than the hydrogen ion H
+
concentration in water.

- The hydronium ion H3O
+
is simply a hydrogen ion H
+
attached to a water molecule.

- e.g., sulfuric acid H2SO4 dissociates to form hydrogen and sulfate ions according to the following equation:

H2SO4 H
+
+ SO4
2-

2

Bases

- A base is a compound which produces hydroxide ions or hydroxyl ions OH
-
in water.
- Some bases contain hydroxyl ions (OH
-
) but others do not. Bases that do not contain hydroxide ions will react with water molecules to
form hydroxyl ions (OH
-
).

Ammonia NH3 + H2O NH4
+
+ OH

Methylamine CH3 NH2 + H2O CH3NH3
+
+ OH

Aniline C6H5NH2 + H2O C6H5NH3
+
+ OH

- e.g., sodium hydroxide, NaOH dissociates to form sodium ions and hydroxyl ions according to the following equations:

NaOH Na
+
+ OH
-

- If the concentration of hydrogen ions H
+
(or hydronium ions) exceeds the concentration of hydroxyl ions OH
-
, the solution is acidic.

- If the concentration of hydroxyl ions exceeds the concentration of hydrogen ions (or hydronium ions), the solution is basic or alkaline.

- If the concentrations of two ions are equal, the solution is neutral.




----------------------------

pH

- Since pH has a significant effect on the chemical reactions which are of concern in the operations of nuclear power plants, control of
pH is very important in the operations of the plants.

The pH of a solution is defined as:

pH = - log {H
+
} - log [H
+
]

{H
+
} [H
+
] = 10
pH


The pOH of a solution is defined as:

pOH = - log {OH
-
} - log [OH
-
]

[OH
-
] {OH
-
} = 10
-pOH


Since
{H
+
}{OH
-
} = 1 x 10
-14


pH + pOH = 14

Pure water is neutral (pH = 7) at 25C.

pH + pOH = 7 + 7 = 14
7-Acid and Base_S11
3

Example: What is the hydrogen ion concentration [H
+
] and the hydroxyl ion concentration
[OH
-
] in a solution with a pH of 5.5? Ignore the ionic strength effect.

a) [H
+
] {H
+
} = 10
-pH
= 10
-5.5
= 3.16 x 10
-6
M (moles/L)

b) K
W
= {H
+
}{OH
-
} [H
+
] [OH
-
] = 10
-14


[OH
-
] = 10
-14
/[H
+
] = 10
-14
/ (3.16 x 10
-6
) = 3.16 x 10
-9


or

pH + pOH = 14; thus pOH = 14 pH = 14 5.5 = 8.5

[OH
-
] {OH
-
} = 10
-pOH
= 10
8.5
= 3.16 x 10
-9
M (moles/L)


Fig 1-9 shows the pH of various common substances.


Neutralization

- the reaction of the hydrogen ions H
+
(or hydronium ion, H3O
+
) of an acid and the hydroxyl ions OH
-
of a base to form undissociated
molecules of water.
- e.g., when dilute solutions of hydrochloric acid HCl and sodium hydroxide NaOH are mixed, the following reaction occurs:

H3O
+
+ Cl
-
+ Na
+
+ OH


2H2O + Na
+
+ Cl
-

--------------------------

Acid dissociation equilibrium constant, K
a
(greater is Ka, greater is acidity)

HCl H
+
+ Cl
-


{H
+
}{Cl
-
}
K
eq
= --------------- = K
a
K
a
= acid dissociation equilibrium constant
{HCl }
K
a
= 10
3

pK
a
= 3 (pKa = - log Ka)

H
2
SO
4
H
+
+ HSO
4
-
pKa
1
= 3

HSO
4
-
H
+
+ SO
4
-
pKa
2
= +1.96

{H
+
}{HSO
4
-
}
Ka
1
= -----------------

Ka
1
= 10
3
= 1
st
acid dissociation equilibrium constant
{H
2
SO
4
} pKa
1
= 3

{H
+
}{SO
4
-
}
Ka
2
= ----------------

Ka
2
= 10
-1.96
= 2
nd
acid dissociation equilibrium constant
{HSO
4
-
} pKa
2
= +1.96

4
Base dissociation equilibrium constant, K
b


NaOH Na
+
+ OH
-
(pKa = 14.77)


{Na
+
}{OH
-
}
K
eq
= ----------------- = K
b
K
b
= base dissociation equilibrium constant
{NaOH } K
b
= 1 since pK
b
= 0

The large K
a
values indicate that the acid has a strong tendency to donate a proton to water; i.e.,
it is a strong acid.

The large K
b
values indicate that the substance has a strong tendency to accept a proton from
water; i.e., it is a strong base. (SJ, p. 90-91)


1. Strong Acid vs. Strong Base

a. Strong Acids
- usually means it dissociate (or ionize) completely (almost completely)
e.g., Table 4-1

Perchloric acid HClO
4
pKa = 7
HCl pKa = 3
H
2
SO
4
pKa = 3
HNO
3
pKa = 0

Hydronium ion

H
3
O
+

pKa = 0



b. Strong Base
- usually means it dissociate (or ionize) completely
- e.g.,
Sodium hydroxide NaOH pKa = 14.77
Potassium hydroxide KOH pKa = 16

(Note: pKa + pK
b
= 14)

2. Weak Acids - partial dissociation

CH
3
COOH acetic acid (HAc) pKa =
HCOOH formic acid pKa =
H
2
CO
3
carbonic acid pKa =
H
2
S hydrogen sulfide pKa =
HCN hydrocyanic acid pKa =
NH
4
+
ammonium pKa =

* Strong acid to weak acid series is really a continuum (see pages 90 & 91 in SJ)

7-Acid and Base_S11
5

Example: If you put 10
-3
moles HCl in 1 L of water, HCl ionizes completely in water. What
will be pH of the water? Neglecting the ionic strength effect. pKa of HCl = 6.1

HCl H
+
+ Cl
-

10
-3
M 10
-3
M 10
-3
M

H
2
O H
+
+ OH
-

10
-7
10
-7


pH = - log {H
+
} - log [H
+
] = - log [10
-3
] = 3 Thus, 10
-3
M HCl gives pH 3.


If you put H2SO4 in water, H2SO4 ionizes in water (pKa1 = -3, pKa2 = +1.96)

H2SO4 H
+
+ HSO4
-
pKa1 = -3

HSO4
-
H
+
+ SO4
-
pKa2 = +1.96

only the first H
+
is strong


Example: If you put 10
-3
mole of NaOH in 1 L of water, NaOH dissociates completely. What
will be pH of the water? Neglecting the ionic strength effect.

NaOH Na
+
+ OH
-

10
-3
10
-3
10
-3


H
2
O H
+
+ OH
-

10
-7
10
-7


pOH = - log {OH
-
} - log [OH
-
] = - log [10
-3
] = 3

pOH + pH = 14

pH = 14 pOH

pH = 14 - 3 = 11 Thus, 10
-3
M NaOH gives pH 11.




Example: Calculate the pH of the following solutions (advanced, do it later).

Perchloric acid, HClO
4
(pKa = 7)

a) 1 x 10
-3
M HClO
4

b) 1 x 10
-8
M HClO
4






6
(Solution)

a) For 1 x 10
-3
M HClO
4


HClO
4
H
+
+ ClO
4

H
2
O H
+
+ OH
-


[H
+
][ClO
4

]
Ka = ------------------ = 1 x 10
7
(1)
[HClO
4
]

K
w
= [H
+
][OH
-
] = 10
-14
(2)

Mass Balance
C
T, ClO4

= [HClO
4
] + [ClO
4

] = 10
-3
(3)

Charge Balance
[H
+
] = [ClO
4

] + [OH
-
] (4)

From the mass balance (3), C
T, ClO4

= [HClO
4
] + [ClO
4

] = 10
-3


Since HClO
4
is a very strong acid, it completely dissociates, [HClO
4
] is negligible


C
T, ClO4

= [ClO
4

] = 10
-3


From charge balance (4), [H
+
] = [ClO
4

] + [OH
-
]

K
w

[H
+
] = [ClO
4

] + ----------
[H
+
]

10
-14

[H
+
] = 10
-3
+ ---------- = 10
-3
+ 10
-11
= 10
-3

10
-3




pH = 3 error < 5%



b) 1 x 10
-8
M - HClO
4


Since C
T
<< 10
-7
, pH is controlled by the K
w
of water. Thus pH ~ 7

Check,

HClO
4
H
+
+ ClO
4

H
2
O H
+
+ OH
-


7-Acid and Base_S11
7
[H
+
][ClO
4

]
K
a
= ------------------ = 1 x 10
7
(1)
[HClO
4
]

K
w
= [H
+
][OH
-
] = 10
-14
(2)

Mass Balance
C
T, ClO4

= [HClO
4
] + [ClO
4

] = 10
-8
(3)

Charge Balance
[H
+
] = [ClO
4

] + [OH
-
] (4)


From the mass balance (3), C
T, ClO4

= [HClO
4
] + [ClO
4

] = 10
-8


Since HClO
4
is a very strong acid, it completely dissociates, [HClO
4
] is negligible


C
T, ClO4

= [ClO
4

] = 10
-8


From charge balance, [H
+
] = [ClO
4

] + [OH
-
]

K
w

[H
+
] = [ClO
4

] + ----------
[H
+
]

10
-14

[H
+
] = 10
-8
+ ---------
[H
+
]

[H
+
]
2
- 10
-8
[H
+
] - 10
-14
= 0


10
-8
+ [(10
-8
)
2
+ (4 x 10
-14
)]
1/2

[H
+
] = --------------------------------------- = 1.05 x 10
-7
pH = 6.98


2


Example: Calculate the pH of the following solutions (advanced, do it later).
Sodium hydroxide, NaOH (totally dissociates)

a) 1x 10
-5
M NaOH

NaOH Na
+
+ OH
-
10
-5


H
2
O H
+
+ OH
-


K
w
= [H
+
][OH
-
] = 10
-14
(1)


8
Mass Balance

C
T, Na
= [Na
+
] = 10
-5
(2)

Charge Balance
[Na
+
] + [H
+
] = [OH
-
] (3)

(10
-5
) + [H
+
] = [OH
-
]

Substitute [OH
-
] = [H
+
] + (10
-5
) into (1)

[H] ([H
+
] + 10
-5
) = 10
-14


[H
+
]
2
+ 10
-5
[H] - 10
-14
= 0

( ) ( ) ( )( )
2
5 5 14
10
10 10 4 1 10
9.999 10
2(1)
H x

+

( = =



pH = 9.00


b) 1x 10
-9
M NaOH


NaOH Na
+
+ OH
-
10
-9


H
2
O H
+
+ OH
-


K
w
= [H
+
][OH
-
] = 10
-14
(1)

Mass Balance
C
T, Na
= [Na
+
] = 10
-9
(2)

Charge Balance
[Na
+
] + [H
+
] = [OH
-
] (3)

(10
-9
) + [H
+
] = [OH
-
]

Substitute [OH
-
] = [H
+
] + (10
-9
) into (1)


[H] ([H
+
] + 10
-9
) = 10
-14


[H
+
]
2
+ 10
-9
[H] - 10
-14
= 0


7-Acid and Base_S11
9
( ) ( ) ( )( )
2
9 9 14
10 8
10 10 4 1 10
9.999 10 9.95 10
2(1)
H x x

+

( = = =



pH = 7.00



3. Conjugate acid vs. Conjugate base

Bronsted-Lowry said:
"Removal of a proton from any acid (weak acid) produces its conjugate base"

a. When hydrocyanic acid HCN is added in water, HCN partially dissociates

Hydrpgen cyanide Cyanide ion
HCN CN
-
+ H
+

weak acid conjugate base

At equilibrium,

{CN
-
}{H
+
}
(1) K
a
= ---------------- = acid dissociation equilibrium constant
{HCN}

K
a
= 10
-9.3
( PK
a
= 9.3 )

b. Addition of a proton (H
+
) to conjugate base produces conjugate acid.
- remove H
+
from H
2
O

- when cyanide ion (CN
-
) is added in water as NaCN, NaCN dissociates completely to
form HCN

NaCN
(aq)
Na
+
+ CN
-


CN
-
+ H
2
O HCN + OH
-
conjugate acid


At equilibrium,

{HCN}{OH
-
} {HCN}{OH
-
}
K
b
= ------------------ = ------------------ = base dissociation equilibrium constant
{CN
-
}{H
2
O} {CN
-
}

K
b
= 10
-4.7
(pK
b
= 4.7) Note pK
b
= - log K
b


See Table 4-1 Acidity and Basicity Constants for substances in Aqueous Solution. (SJ, p. 446)

[10
-3
M NaCN in solution is identical to 10
-3
M NaOH (strong base) plus 10
-3
M HCN (weak acid) ]
10

{CN
-
}{H
+
} {HCN}{OH
-
}
K
a
K
b
= ---------------- ------------------- = {H
+
}{OH
-
} = K
w
= 10
-14
at 20C
{HCN} {CN
-
}

K
a
K
b
= K
w


(10
-9.3
)(10
-4.7
) = 10
-14
or (5.01 x 10
-10
) (2.02 x 10
-5
) = 10
-14


K
w
= water dissociation constant = molar ion product of water

pKa + pK
b
= PKw

9.3 + 4.7 = 14

c. Dissociation of water

H
2
O H
+
+ OH
-


{H
+
}{OH
-
}
Keq = ---------------- = {H
+
}{OH
-
} = K
w
= 10
-14

{H
2
O}

{H
+
}{OH
-
} = K
w
= 10
-14
at 20C


a. NH
4
+
is added in water as NH
4
Cl

NH
4
Cl NH
4
+
+ Cl
-


NH
4
+
NH
3(aq)
+ H
+

weak acid conjugate
base

(NH
3
consumes H
+
)

{NH
3
}{H
+
}
Ka = --------------- = 10
-9.3

{NH
4
+
}

- Removal of a proton from acid produces its conjugate base.


b. NH
3
is added in water

NH
3
+ H
2
O NH
4
+
+ OH
-

weak base conjugate
acid


7-Acid and Base_S11
11
{NH
4
+
}{OH
-
}
K
b
= ------------------- = 10
-4.7

{NH
3
}

- Addition of a proton to conjugate base produces conjugate acid.


c. K
a
K
b
= (10
-9.3
) (10
-4.7
) = 10
-14
= K
w


--------------------------------------------------------

Q: How do you add a conjugate base like CN
-
to a system?
A: Add as the salt of a weak acid - a conjugate base is the salt of the weak acid.


HCN CN
-
+ H
+

weak acid conjugate base


{H
+
}{CN
-
}
Keq = -------------- = Ka = 10
-9.3
PKa = 9.3 at 25C
{HCN}

Ka = acid dissociation constant (greater is Ka, greater is acidity)


Add CN
-
as NaCN

NaCN Na
+
+ CN

CN

+ H2O HCN + OH

weak base conjugate acid

{HCN}{OH

}
Keq = -------------------- = Kb = 10
4.7

{CN

}


PKa = 4.7 at 25 C

Kb = base dissociation constant (greater is Kb, greater is the weak base)


{H
+
}{CN

} {HCN}{OH

}
Ka Kb = --------------- --------------------
{HCN} {CN

}

= { H
+
}{OH

} = Kow

= (10
-9.3
) (10
4.7
) = 10
14


Kw = water dissociation constant = molal ion product of water


12

-------------------------
NSEN

3-3.1 Acid-Base Equilibria of Dilute Solutions (Cohen, p. 44)

Since free protons cannot be expected to exist in solution to any significant extent, the acidic or basic properties of a solute cannot be realized
unless the solvent itself possesses acid or basic properties; i.e., can accept or donate protons. Thus, the general case for significant acid or basic
solutions must be written


HA H
+
+ A
-

A
-
+ H2O HA + OH
-

--------------------------------------------------------------
HA + H2O HA + H
+
+ OH
-


- Water can act as both a proton acceptor and a proton donor (amphiprotic) and therefore its solution can show both acidic and basic properties.

Water dissociates to protons (hydronium) and hydroxyl ions

2H2O H3O
+
+ OH
-

hydronium

with similar reaction for heavy water.

The equilibrium for this reaction is written

{H3O
+
}{OH
-
} H3O
+
[H3O
+
] OH
-
[OH
-
]
Kw = -------------------- = ---------------------------------
{H2O}
2
H2O
2
[H2O]
2


a H3O
+
C a OH
-

= ------------------------ (3.12)
a
2
H2O

where or a refer to activity coefficient

For dilute solutions, up to 10
-4
M, the activities are nearly equal to the molal concemtrations, m, and the water activity is essentially constant.
Thus,

Kw = [H3O
+
] [OH
-
] or mH+ C mOH- = Kw (3.13)


Table 3.1 and Fig. 3.2 present three sets of data for the molal ion product of pure water.


Table 3.1 Molar Ion Product of Water (Cohen, 1980)
Jones (1958) Noyes (1910) Harned and Owen (1950)
Temperature Temperature Temperature
o
F
o
C Kw x 10
14 o
F
o
C Kw x 10
14 o
F
o
C Kw x 10
14
75 24 0.9 64.4 18 0.64 64.4 18 0.57
200 93 43 212 100 55 212 100 54.6
300 149 208 313 156 268 313 156 222
400 204 500 424 218 645 424 218 403
480 249 645 583 306 340 583 306 308
540 282 628

* Some possibility exists that the experimental results of Noyes et al. (1910) may be in error (Cohen, 1980).


log
.
. . ( ) Kw
T
T = +
447099
60875 00170607
(3.14)

where T = temperature (F, R ?)

????? The computed results using the above Eqn.(3.14) do not match with the data presented in Table 3.1 ?????
7-Acid and Base_S11
13




Figure 3.2. Molal ion product of water.

14

Solving Acid-Base Equilibrium Problems

Steps to solve equilibrium problems.

Write:

1. Equilibrium Reactions and Equations

2. Mass balance: C
T
= concentration of all species (of the compounds involved)

3. Charge balance: (positive charge) = (negative charge)

4. Proton balance (proton condition): (proton gainer) = (proton loser)

Summation of all species Summation of all species
that gain a proton = that lose a proton
in solution in solution




Example: Soda ash (Na
2
CO
3
) is added to pure water.

Na
2
CO
3
2 Na
+
+ CO
3
2-


1. a. Equilibrium reactions:

H
2
CO
3
H
+
+ HCO
3
-
HCO
3
-
H
+
+ CO
3

2-

H
2
O H
+
+ OH
-

b. Equilibrium equations:

{H
+
}{HCO
3
-
}
K
a1
= ------------------ (1)
{H
2
CO
3
}

{H
+
}{CO
3
2-
}
K
a2
= ----------------- (2)
{HCO
3
-
}

K
w
= {H
+
} {OH
-
} (3)


2. Mass balance:

C
T,CO3
= [H
2
CO
3
] + [HCO
3
-
] + [CO
3
2-
] (4)


7-Acid and Base_S11
15


3. Charge balance:

[Na
+
] + [H
+
] = 2 [CO
3
2-
] + [HCO
3
-
] + [OH
-
] (5)


4. Proton condition: zero level / reference species; CO
3
2-
, H
2
O

2 [H
2
CO
3
] + [HCO
3
-
] + [H
+
] = [OH
-
] (6)


Note H
+
is same as H
3
O
+


6 unknowns and 6 equations


Note:

HCO
3

+ H
2
O H
2
CO
3
+ OH

(1)


CO
3

2
+ H
2
O HCO
3
-
+ OH

(2)


[H
2
CO
3
][OH

]
K
b1
= --------------------- (1)
[HCO
3

] [H
2
O]


[HCO
3

][OH

]
K
b2
= --------------------- (2)
[CO
3
2
] [H
2
O]

16


Example : NaAsO
2
(herbicide) is added to distilled water.

NaAsO
2
Na
+
+ AsO
2

1) Equilibrium reactions

AsO
2

+ H
2
O HAsO
2
+ OH


H
2
O H
+
+ OH



[HAsO
2
] [OH

] K
w

Equilibrium eqn: K
b
= ------------------- = ------ (1)
[AsO
2

] [H
2
O] K
a


(since K
a
K
b
= K
w
)

Kw = [H
+
] [OH

] (2)

2) Mass balance: C
T,As
= [AsO
2

] + [HAsO
2
] (3)

3) Charge balance: [H
+
] + [Na
+
] = [OH

] + [AsO
2

] (4)

4) Proton condition: zero level (reference level); AsO
2
-
, H
2
O

[HAsO
2
] + [H
+
] = [OH

] (5)

5 unknowns and 5 equations

Note:
HAsO
2
H
+
+ AsO
2

[ AsO
2

] [H
+
]
K
a
= -------------------
[HAsO
2
]


AsO
2

+ H
2
O HAsO
2
+ OH



[HAsO
2
] [OH

]
K
b
= ---------------------
[AsO
2
-
] [H
2
O]

[H
+
][ AsO
2

] [HAsO
2
] [OH

]
K
a
K
b
= ---------------------------------------- = [H
+
] [OH

] = Kw
[HAsO
2
] [AsO
2
-
] [H
2
O]
1


7-Acid and Base_S11
17

Three methods for solving acid-base equilibrium problems:

1) Exact solution (solve a set of algebraic equations simultaneously).
2) Approximation solutions (make assumptions, then solve algebraic equations within 5% error)
3) Graphical solution (approximation method)


General Equation for the pH of a weak acid - exact solution (Butler p. 120)

Based on K
a


HA H
+
+ A
-

H
2
O H
+
+ OH
-


1) Equilibrium
- assume effect of ionic strength is negligible; i.e., = 1 for simplicity

Acid dissociation constant

[H
+
][A
-
]
Ka = ----------- (1)
[HA]

Molal ion product of water

Kw = [H
+
][OH
-
] (2)

2) Mass balance on A
C
T, A
= [A
-
] + [HA] (3)

3) Charge balance:
[H
+
] = [A
-
] + [OH
-
] (4)

4) Proton balance (Proton condition):
Reference species (zero level species): HA, H
2
O

[H
+
] = [A
-
] + [OH
-
] (5)


From the mass balance eqn (3):

[HA] = C
T, A
- [A
-
] (3)

Substitute (3) into (1) and solve for [A
-
]:

[H
+
] [A
-
]
K
a
= -----------------
(C
T, A
) - [A
-
]

18



Solve for [A
-
]:

K
a
(C
T, A
) - K
a
[A
-
] = [H
+
] [A
-
]
[A
-
] ([H
+
] + Ka) = K
a
(C
T, A
)

Ka (C
T, A
)
[A
-
] = ----------------- (1)
[H
+
] + K
a


Substitute (1) into the charge balance (4)

K
a
(C
T, A
)
[H
+
] = -------------- + [OH
-
] (7)
[H
+
] + Ka


Solve for C
T, A


( [H
+
] - [OH
-
] ) ([H
+
] + K
a
)
C
T, A
= ---------------------------------
K
a


[H
+
] + Ka
= ( [H
+
] - [OH
-
] ) (-----------------)
Ka

K
w
[H
+
]
= ([H
+
] - -------) ( ------ + 1 ) (8)
[H
+
] K
a


[H
+
] K
w

C
T, A
= (1 + ------- ) ([H
+
] - ------- ) (9)
K
a
[H
+
]

This is a general (exact) equation for pH of a weak acid.

7-Acid and Base_S11
19

Based on K
b


HA H
+
+ A
-

A
-
+ H
2
O HA + OH
-

H
2
O H
+
+ OH
-


Note:
[H
+
][A
-
] [HA][OH
-
]
K
a
K
b
= ------------ ---------------- = [H
+
] [OH
-
] = K
w

[HA] [A
-
]

K
w

k
b
= ---------
K
a


1) Equilibrium
- assume effect of ionic strength is negligible; i.e., = 1 for simplicity

[HA] [OH
-
] Kw
Kb = --------------- = ------- (1)
[A
-
] Ka

Kw = [H
+
][OH
-
] (2)

2) Mass balance on A
C
T, A
= [A
-
] + [HA] (3)

3) Charge balance:
[H
+
] = [A
-
] + [OH
-
] (4)

4) Proton balance (Proton condition):
Reference species (zero level species): HA, H
2
O

[H
+
] = [A
-
] + [OH
-
] (5)


From the mass balance eqn (3):
[HA] = C
T, A
- [A
-
] (3)
Substitute (3) into (1) and solve for [HA]:

(C
T, A
- [A
-
] ) [OH
-
]
K
b
= ---------------------------- (6)
[A
-
]

Solve for [Ac
-
]:
K
b
[A
-
] = (C
T, A
- [A
-
] ) [OH
-
] = C
T, A
[OH
-
]- [A
-
] [OH
-
]
K
b
[A
-
] + [A
-
] [OH
-
] = [A
-
] (K
b
+ [OH
-
] ) = C
T, A
[OH
-
]


20

C
T, A
[OH
-
]
[A
-
] = ----------------- (1)
K
b
+ [OH
-
]

Substitute (1) into the charge balance (4)

C
T, A
[OH
-
]
[H
+
] = ----------------- + [OH
-
] (7)
K
b
+ [OH
-
]

Solve for C
T, A

C
T, A
[OH
-
]
[H
+
] - [OH
-
] = -----------------
K
b
+ [OH
-
]

C
T, A
[OH
-
] = ( [H
+
] - [OH
-
] ) (K
b
+ [OH
-
])

K
b

C
T, A
= ( [H
+
] - [OH
-
] ) (--------- + 1)
[OH
-
]

Kw K
b
[H
+
]
C
T, A
= ([H
+
] - -------) ( ----------- + 1 ) (8)
[H
+
] Kw

Or from the previous En:

[H
+
] Kw
C
T, A
= (1 + ------- ) ([H
+
] - ------- )
Ka [H
+
]

[H
+
] Kw
= (1 + ----------- ) ([H
+
] - ------- )
K
w
/ k
b
[H
+
]

k
b
[H
+
] Kw
= (1 + ----------- ) ([H
+
] - ------- ) (9)
K
w
[H
+
]

This is a general (exact) equation for pH of a weak acid.


For weak base (Sato)

Based on K
b


AOH A
+
+ OH
-

H
2
O H
+
+ OH
-


7-Acid and Base_S11
21

Note:

1) Equilibrium
- assume effect of ionic strength is negligible; i.e., = 1 for simplicity

[A
+
] [OH
-
]
Kb = --------------- (1)
[AOH]

Kw = [H
+
][OH
-
] (2)

2) Mass balance on A
C
T, A
= [A
+
] + [AOH] (3)

3) Charge balance:
[A
+
] + [H
+
] = [OH
-
] (4)


From the mass balance eqn (3):
[AOH] = C
T, A
- [A
+
] (3)
Substitute (3) into (1) and solve for [HA]:

[A
+
] [OH
-
]
K
b
= ------------------
C
T, A
- [A
+
]

Solve for [A
+
]:
K
b
(C
T, A
- [A
+
]) = [A
+
] + [OH
-
]
K
b
C
T, A
- K
b
[A
+
] = [A
+
] + [OH
-
]
K
b
C
T, A
= [A
+
] [OH
-
] + K
b
[A
+
]
= [A
+
] ([OH
-
] + K
b
)

K
b
C
T, A

[A
+
] = ----------------- (1)
K
b
+ [OH
-
]

Substitute (1) into the charge balance (4)

K
b
C
T, A

[H
+
] + ----------------- = [OH
-
] (5)
K
b
+ [OH
-
]

Solve for C
T, A

K
b
C
T, A

[OH
-
] [H
+
] = -----------------
K
b
+ [OH
-
]



22


[OH
-
] + K
b

C
T, A
= ( [OH
-
] [H
+
] ) (------------------)
K
b


[OH
-
]
= ( [OH
-
] [H
+
] ) (----------- + 1 )
K
b


Kw Kw / [H
+
]
= ( ------ [H
+
] ) (-------------- + 1 )
[H
+
] K
b


Kw Kw
= (------- [H
+
] ) ( ----------- + 1 ) (6)
[H
+
] K
b
[H
+
]

This is a general (exact) equation for pH of a weak base.

Cohen (1980, p. 50) gives the following eqn:

K
w
Kw
C
T, A
= (1 + ------------ ) (-------- [H
+
] ) (7)
k
b
[H
+
] [H
+
]

7-Acid and Base_S11
23

1. Exact solution

Example: Find the pH and chemical species concentrations of 0.01 M CH
3
COOH (acetic acid,
HAc):

CH
3
COOH CH
3
COO

+ H
+


HAc Ac
-
+ H
+


Neglect ionic strength effect ( = 1 for simplicity).

Note: We know
HAc is acid, thus pH < 7
HAc is weak acid, thus pH > 2 (noting that strong acid such as 0.01 M HCl has pH ~ 2)
Thus, we expect pH of HAc is 2 < pH < 7


(Solution)

1) Equilibrium

HAc H
+
+ Ac

pKa = 4.7
H
2
O H
+
+ OH

pKw = 14

a) Acid dissociation equilibrium eqn:
- assume effect of ionic strength is negligible; i.e., = 1 for simplicity

[H
+
] [Ac

]
Ka = --------------- = 10
4.7
= 2.00 x 10
5
(1)
[HAc]

b) Water equilibrium eqn:

Kw = [H
+
][OH

] = 1 x 10
14
(2)


2) Mass balance on Ac, C
T, Ac


C
T, Ac
= [Ac

] + [HAc] = 0.01 (3)

3) Charge balance: positive charge species = negative charge species

[H
+
] = [Ac

] + [OH

] (4)

24

4) Proton balance (Proton condition):

all species that gain a proton = all species that lose a proton
( proton gainers = proton losers)

Reference species (zero level species): HAc, H
2
O

[H
+
] = [Ac

] + [OH

] (5)

Note H
+
is same as H
3
O
+


We have 4 unknowns and 4 equations. Now solve the set of algebraic equations (1)-(4) or (5),
simultaneously.

From Eq. (2)
[ ]
[ ]
OH
x
H

+
=
1 10
14


Then substitute [OH
-
] into the proton condition Eq. (5)

[ ] [ ]
[ ]
H Ac
x
H
+

+
= +
1 10
14
and solve for [Ac
-
]

[ ] [ ]
[ ]
Ac H
x
H
+

+
=
1 10
14
(6)

Substitute Eq (6) into the mass balance En (3):

[ ]
[ ]
[ ]
001
1 10
14
. = +

+
HAc H
x
H


and solve for [HAc]

[ ]
[ ]
[ ]
HAc H
x
H
=

+
0 01
1 10
14
. (7)

Substituting Eqs. (6) and (7) into Eq. (1) yields

7-Acid and Base_S11
25
[ ] [ ]
[ ]
[ ]
[ ]
K
H H
x
H
H
x
H
x
a
=

=
+ +

+
+

1 10
001
1 10
2 10
14
14
5
.


2x10
-7
- 2 x 10
-5
[H
+
] + 2 x 10
-19
/[H
+
] = [H
+
]
2
1 x 10
-14


[H
+
]
2
+ 2 x 10
-5
[H
+
] 2x10
-7
2 x 10
-19
/[H
+
] = 0

[H
+
]
3
+ 2 x 10
-5
[H
+
]
2
2x10
-7
[H
+
] 2 x 10
-19
= 0


This is a third degree polynomial equation. Use methods such as trial and error solution or
numerical method (e.g., Newton-Raphson, Jacobian iteration, and Birge-Vietta).

[H
+
] = 10
3.36


[OH
-
] = Kw / [H
+
] = 10
-14
/ 10
3.36
= 2.291 x 10
11


Using Eq. (6), solve for Ac
-


[ ] [ ]
[ ]
Ac H
x
H
+

+
=
1 10
14


[Ac
-
] = 10
3.36
- (10
-14
/ 10
3.36
) = 4.365 x 10
-4



From mass balance eq. (3)

[HAc] = 0.01 [Ac
-
] = 9.563 x 10
-3



Summary

[H
+
] = 10
3.36
thus, pH = log [H
+
] = 3.36

[OH
-
] = 2.291 x 10
11

[Ac
-
] = 4.365 x 10
-4

[HAc] = 9.563 x 10
-3


26


2. Approximate solution

Example : Find the pH and chemical species concentrations of 0.01 M CH
3
COOH (acetic acid,
HAc):
CH
3
COOH CH
3
COO

+ H
+


HAc Ac
-
+ H
+


Neglect ionic strength effect ( = 1).


(Solution)

1) Equilibrium

HAc H
+
+ Ac

(pKa = 4.7)
H
2
O H
+
+ OH

(pKw = 14)

[H
+
] [Ac

]
Ka = --------------- = 10
4.7
= 2.00 x 10
5
(1)
[HAc]

Kw = [H
+
][OH

] = 1 x 10
14
(2)


2) Mass balance on Ac
C
T, Ac
= 0.01 = [Ac

] + [HAc] (3)

3) Charge balance:

positive charge species = negative charge species

[H
+
] = [Ac

] + [OH

] (4)


4) Proton balance (Proton condition): proton gainers = proton losers

Reference species (zero level species): HAc, H
2
O

[H
+
] = [Ac

] + [OH

] (5)

7-Acid and Base_S11
27

Assumptions:

i) [H
+
] >> [ OH
-
] because HAc is acid (approximately 100 x greater )

ii) [HAc] >> [Ac
-
] because HAc is weak acid (Ka is very small)


a. Solution using assumption (i)

From proton condition Eq. (5)

[H
+
] = [Ac

] + [OH

]

from assumption (i), [OH

] ~ 0;

[H
+
] = [Ac

]

Let [H
+
] = [Ac
-
] = x (6)

From mass balance Eq. (3),
C
T, Ac
= 0.01 = [Ac
-
] + [HAc]

0.01 = x + [HAc]

thus [HAc] = 0.01 x (7)

Substituting Eqs (6) and (7) into the equilibrium eqn (1):

[H
+
] [Ac
-
] x
2

Ka = --------------- = ------------ = 2.00 x 10
-5

[HAc] 0.01 x

Then, solve for x

2x10
-7
2 x 10
-5
x = x
2


x
2
+ 2 x 10
-5
x 2 x 10
-7
= 0

This is a quadratic equation, and can be solved.



Note: If a general quadratic equation is a x
2
+ bx + c = 0, a general solution is

x
b b ac
a
=

2
4
2



28

x
x x x
x x
=

=



2 10 2 10 4 1 2 10
2 1
2 10 89465 10
2
5 5 2 7
5 4
( ) ( )( )
( )
.


x = - 4.57 x 10
-4
and 4.37 x 10
-4
only one answer is correct

x = [H
+
] = 4.37 x 10
-4


[OH
-
] = 10
-14
/ 4.37 x 10
-4
= 2.29 x 10
11


[Ac
-
] = 4.37 x 10
-4


[HAc] = 0.01 - 4.37 x 10
-4
= 9.56 x 10
-3


* Check the assumption using charge balance eqn (4)

[H
+
] = [Ac
-
] + [OH
-
] (4)

(4.37 x 10
-4
) = (4.37 x 10
-4
) + (2.29 x 10
11
)


% error
right hand side left hand side
left hand side
x =

100


(4.37 x 10
-4
) + (2.29 x 10
11
) - (4.37 x 10
-4
)
% error = -------------------------------------------------------- x 100
(4.37 x 10
-4
)

= 5.2 x 10
-6
< 5 % thus the assumption is acceptable.

Summary

[H
+
] = 4.37 x 10
-4
thus, pH = log [4.37 x 10
-4
] = 3.36
[OH

] = 2.29 x 10
11

[Ac

] = 4.37 x 10
-4

[HAc] = 9.56 x 10
-3





7-Acid and Base_S11
29

b) Solution using assumptions (i) and (ii)

From proton condition eqn (5),

[H
+
] = [Ac
+
] + [OH
-
] and

from assumption (i), [OH
-
] ~ 0;

[H
+
] = [Ac
-
]

Let [H
+
] = [Ac
-
] = x (a)

From mass balance Eq. (3),

C
T, Ac
= 0.01 = [Ac
-
] + [HAc] and

assumption (ii), [HAc] >> [Ac
-
] ;

0.01 = [HAc] (b)

Substituting (a) and (b) into the acid dissociation equilibrium eqn (1) yields

[H
+
] [Ac
-
] x
2

Ka = ------------- = ------- = 2.00 x 10
-5

[HAc] 0.01

then solve for x: x = [H
+
] = [Ac
-
] = 4.47 x 10
-4


[OH
-
] = 10
-14
/ 4.47 x 10
-4
= 2.24 x 10
11

[HAc] = 0.01


* Check the assumption using charge balance eqn (4)

[H
+
] = [Ac
-
] + [OH
-
] (4)

(4.47 x 10
-4
) = (4.47 x 10
-4
) + (2.24 x 10
11
)


% error
right hand side left hand side
left hand side
x =

100


(4.47 x 10
-4
) + (2.24 x 10
11
) - (4.47 x 10
-4
)
% error = -------------------------------------------------------- x 100
(4.47 x 10
-4
)

= 2.3 x 10
-9
< 5 % thus the assumption is acceptable.
30


Summary

[H
+
] = 4.47 x 10
-4
thus, pH = log [4.47 x 10
-4
] = 3.35

[OH
-
] = 2.24 x 10
11

[Ac
-
] = 4.47 x 10
-4

[HAc] = 0.01

Overall Summary:

1) Exact solution, pH = 3.36
2) Based on assumption (i), pH = 3.36
3) Based on assumptions (i) and (ii), pH = 3.35
7-Acid and Base_S11
31




A guide for making approximations

1. Look at the size of the concentration (C
T
). If it is small compared to 10
-7
, only [H
+
] and
[OH
-
] will be predominant and the pH will be near 7.
2. If the concentration is large compared to 10
-7
, look at Ka.
3. If Ka is small compared to 10
-7
, the acid will never become completely dissociated, and a
reasonable approximation is that [HA] is large compared to [A
-
]. Try this. If it doesnt
work, solve the exact equations.
4. If Ka is large compared to 10
-7
, look at the size of the concentration compared to Ka.
5. If the concentration is small compared to Ka but large compared to 10
-7
, complete
dissociation may be a good approximation. Try this. If it doesnt work, solve the exact
equations.
6. If the concentration is large compared to Ka, [H
+
] will certainly be large compared to
[OH
-
]. In addition, a reasonable approximation is slight dissociation, [HA] predominant.
Try this. If it doesnt work, use the exact mass balance.


Flow Chart for Weak Acid Approximations

C
T
<< 10
-7
pH ~7.0
C
T
>> 10
-7
Ka << 10
-7
Assume HA >> A
-
Ka >> 10
-7
C
T
<< Ka
Assume HA << A
-
C
T
>>Ka
Assume H
+
>> OH
-
and/or HA >> A
-
C
T
compared to 10
-7
Ka compared to 10
-7
C
T
compared to Ka



32


Example: (SJ, p.192, 4.14.3) Arsenious acid is a weak acid:

HAsO
2
<==> H
+
+ AsO
2
-
PKa = 9.92 Ka = 10
-9.22


If 10
-3
moles of the herbicide NaAsO
2
, are added to 1 liter of distilled water at 25C, what is the
resulting pH? Determine by solving the appropriate set of equations analytically (using
approximate method).

NaAsO
2
Na
+
+ AsO
2
-

AsO
2
-
+ H
2
O HAsO
2
+ OH
-
H
2
O H
+
+ OH
-

Equilibrium:

[HAsO
2
][ OH
-
] K
w
10
-14

K
b
= ----------------------- = ------ = ----------
[AsO
2
-
] Ka 10
-9.22


= 10
-4.78
(1)

Kw = [H
+
][OH
-
] = 10
-14
(2)

Mass Balance:
C
T, AsO
2
= [HAsO
2
] + [AsO
2
-
] = 10
-3
(3)

Charge Balance:
[H
+
] + [Na
+
] = [OH
-
] + [AsO
2
-
] (4)

Proton Condition: (zero level sp. Na
+
, AsO
2
-
, H
2
O )
[HAsO
2
] + [H
+
] = [ OH
-
] (5)


Assumptions:
Because the solution is basic, [H
+
] << [OH
-
]

From proton condition (5),
[HAsO
2
] = [OH
-
] = x (5)
From mass balance (3),
C
T, AsO
2
= [HAsO
2
] + [AsO
2
-
] = 10
-3


[AsO
2
-
] = 10
-3
- [HAsO
2
] = 10
-3
- x (3)

7-Acid and Base_S11
33



Substituting (3) and (5) into (1) gives

[HAsO
2
][ OH
-
] x
2


K
b
= ---------------------- = ----------- = 10
-4.78
(1)
[AsO
2
-
] 10
-3
- x

x = 1.37 x 10
-4


[HAsO
2
] = [OH
-
] = 1.37 x 10
-4

[AsO
2
-
] = 10
-3
- [HAsO
2
]
= 10
-3
- (1.37 x 10
-4
) = 8.63 x 10
-4


Kw 10
-14

[H
+
] = -------- = ---------------- = 7.30 x 10
-11

[OH
-
] 1.37 x 10
-4


pH = 10.14

Check the assumptions using Charge Balance Eq. (4)

[H
+
] + [Na
+
] = [OH
-
] + [AsO
2
-
] (4)

(7.30 x 10
-11
) + (1 x 10
-3
) = (1.37 x 10
-4
) + (8.63 x 10
-4
)

1 x 10
-3
= 1 x 10
-3


Error < 5%



34

Example (SJ, p.193, 4.14.7) What pH results when 10
-4
mole of NaH
2
PO
4
are added to 1 liter of
distilled water? The temperature = 25C; assume that = 10
-2
after the addition. Compare the
value obtained when ionic strength effects are taken into account with that calculated when it is
neglected. (See Fig. 3-4 for activity coefficients.)


NaH
2
PO
4
Na
+
+ H
2
PO
4
-

10
-4
10
-4


H
3
PO
4
H
2
PO
4

+ H
+

H
2
PO
4

HPO
4
2
+ H
+

HPO
4
2
PO
4
3
+ H
+

H
2
O H
+
+ OH


Equilibrium:

{H
2
PO
4

} {H
+
}
K
a1
= -------------------- = 5.9 x 10
-3
(1)
{H
3
PO
4
}

{HPO
4
2
}{H
+
}
K
a2
= -------------------- = 6.2 x 10
-8
(2)
{H
2
PO
4

}


{PO
4
3
} {H
+
}
K
a3
= ------------------- = 4.8 x 10
-13
(3)
{HPO
4
2
}

K
w
= {H
+
}{OH

} = 10
14
(4)


Mass balance:
C
T
= [H
3
PO
4
] + [H
2
PO
4

] + [HPO
4
2
] + [PO
4
3
] = 1 x 10
-4

(5)
Charge balance:
[Na
+
] + [H
+
] = [H
2
PO
4

] + 2[HPO
4
2
] + 3[PO
4
3
] + [OH
-
]
(6)

Proton condition:
Reference level or zero level : H
2
O, H
2
PO
4

[H
3
PO
4
] + [H
+
] = [HPO
4
2
] + 2[PO
4
3
] + [OH

] (7)



7-Acid and Base_S11
35

Assumptions:

1) the solution is acidic because NaH
2
PO
4
forms multi proton compounds.
2) The dominant reaction will probably be (2) because the compound is added as H
2
PO
4

.
3) [HPO
4
2
] >> [PO
4
3
] because K
a3
<< K
a2

4) [HPO
4
2
] >> [H
3
PO
4
] because K
a2
<< K
a1



From proton condition (7),
neg neg neg

[H
3
PO
4
] + [H
+
] = [HPO
4
2
] + 2[PO
4
3
] + [OH

]

[H
+
] = [HPO
4
2
]

From mass balance,
neg neg

C
T
= [H
3
PO
4
] + [H
2
PO
4

] + [HPO
4
2
] + [PO
4
3
] = 1 x 10
-4


C
T
= [H
2
PO
4

] + [HPO
4
2
] = 1 x 10
-4


[H
2
PO
4

] = 1 x 10
-4
[HPO
4
2
]


i) when = 0, = 1

Let [H
+
] = [HPO
4
2
] = x (a)
[H
2
PO
4

] = 1 x 10
-4
[HPO
4
2
] = 1 x 10
-4
x (b)

Substituting (a) and (b) yields

[HPO
4
2
] [H
+
] x
2

K
a2
= --------------------- = -------------------- = 6.2 x 10
-8

[H
2
PO
4

] (1 x 10
-4
) x


x
2
+ 6.2 x 10
8
x 6.2 x 10
12
= 0

6
12 2 8 8
10 459 . 2
2
) 10 2 . 6 ( 4 ) 10 2 . 6 ( 10 2 . 6

=
+
= x
x x x
x

[H
+
] = [HPO
4
2
] = x = 2.459 x 10
-6


pH = - log (2.459 x 10
-6
) = 5.61 and pOH = 8.39

[OH-] = Kw/ [H
+
] = (1 x 10
-14
)/ (2.459 x 10
-6
)

= 4.067 x 10
-9

36




[H
2
PO
4

] = (1 x 10
-4
) x = (1 x 10
-4
) (2.459 x 10
-6
)

= 9.754 x 10
-5


From (1)

[H
2
PO
4

] [H
+
] (9.754 x 10
-5
) (2.459 x 10
-6
)
[H
3
PO
4
] = --------------------- = ------------------------------------
K
a1
5.9 x 10
-3


= 4.065 x 10
-8


From (3)

K
a3
[HPO
4
2
] (4.8 x 10
-13
) (2.459 x 10
-6
)
[PO
4
3
] = ----------------- = ------------------------------------
[H
+
] (2.459 x 10
-6
)

= 4.8 x 10
-13


Check:

Using charge balance (6)

[Na
+
] + [H
+
] = [H
2
PO
4

] + 2[HPO
4
2
] + 3[PO
4
3
] + [OH
-
]

(1 x 10
-4
) + (2.459 x 10
-6
) = (9.754 x 10
-5
) + 2(2.459 x 10
-6
)

+ 3 (4.8 x 10
-13
) + (4.067 x 10
-9
)

(1.0246 x 10
-4
) = (1.02462 x 10
-4
) ---- checked OK


i) when = 10
-2
,


HPO42
[HPO
4
2
]
H
+
[H
+
]
K
a2
= ----------------------------------- = 6.2 x 10
-8
(2)

H2PO4
[H
2
PO
4

]


The activity coefficients are (see note below)

HPO42
= 0.66 (a)

H
+
=
H2PO4
= 0.90 (b)

Substituting (a) and (b) into (2)
7-Acid and Base_S11
37



0.66 [HPO
4
2
] 0.9 [H
+
]
K
a2
= ----------------------------------- (2)
0.9

[H
2
PO
4

]

Let [H
+
] = [HPO
4
2
] = x (c)
[H
2
PO
4

] = 1 x 10
-4
[HPO
4
2
] = 1 x 10
-4
x (d)

0.66 x
2

K
a2
= ------------ = 6.2 x 10
-8

10
-4
x


x
2
+ 9.39 x 10
8
x 9.39 x 10
12
= 0

6
12 2 8 8
10 0177 . 3
2
) 10 39 . 9 ( 4 ) 10 39 . 9 ( 10 39 . 9

=
+
= x
x x x
x

[H
+
] = [HPO
4
2
] = x = 3.0177 x 10
-6


pH = - log (3.0177 x 10
-6
) = 5.52 and pOH = 8.39

[OH

] = Kw/ [H
+
] = (1 x 10
-14
)/ (3.0177 x 10
-6
)

= 4.067 x 10
-9



[H
2
PO
4

] = (1 x 10
-4
) x = (1 x 10
-4
) (3.0177 x 10
-6
)

= 9.698 x 10
-5


From (1)

[H
2
PO
4

] [H
+
] (9.898 x 10
-5
) (3.0177 x 10
-6
)
[H
3
PO
4
] = --------------------- = ------------------------------------
K
a1
5.9 x 10
-3


= 4.960 x 10
-8


From (3)


K
a3
[HPO
4
2
] (4.8 x 10
-13
) (9.698 x 10
-5
)
[PO
4
3
] = ----------------- = ---------------------------------
[H
+
] (3.0177 x 10
-6
)

= 1.543 x 10
-11


38



----------
Note

B a
z A
i
i
i
+
=
1
) (
log
2
10


At 25

C,
A = 0.5085,
B = 0.3281 x 10
8


for H
2
PO
4
,
a
i
= 4.00 x 10
-8
and z = 1
for HPO
4
2,
a
i
= 4.00 x 10
-8
and z = 2
for H
+
, a
i
= 9.00 x 10
-8
and z = 1


17980 . 0
10 ) 10 3281 . 0 )( 10 00 . 4 ( 1
10 ) 2 ( 5085 . 0
log
2 8 8
2 2
42
10
=
+
=

x x
HPO

HPO42
= 10
0.17980
= 0.66


04495 . 0
10 ) 10 3281 . 0 )( 10 00 . 4 ( 1
10 ) 1 ( 5085 . 0
log
2 8 8
2 2
4 2
10
=
+
=

x x
PO H

H2PO4
= 10
0.045
= 0.91

04495 . 0
10 ) 10 3281 . 0 )( 10 00 . 4 ( 1
10 ) 1 ( 5085 . 0
log
2 8 8
2 2
10
=
+
=

+
x x
H

H
+
= 10
0.045
= 0.91














7-Acid and Base_S11
39


------------------------
NSEN

Bases of interest in water reactor

KOH, LiOH, NH4OH

- The bases of interest in water reactor technology are
KOH, LiOH, and NH4OH.

- NaOH is not ordinarily utilized because of problems resulting from activation of
23
Na to
24
Na.

- LiOH has been shown experimentally to be associated at high concentrations, and the same is probably true for KOH at high temperatures.

- NH4OH is a weak base.
- At the normal concentrations of interest (10
-4
M), however, only the dissociation of NH4OH need to be taken into account in computing
solution pH.

Dissociation constants for NH4OH and LiOH are presented in Table 3.2 and Fig. 3.3.

Table 3.2 Dissociation Constants: NH4OH, LiOH, and HSO4
-
(Cohen, 1980)
Jones (1958) Write (1961) Write (1961)
(a) Marshall &
Johns (1966)
NH
4
OH NH
4
OH LiOH HSO
4
-
(
o
F) (
o
C) K
b
x 10
6
K
b
x 10
6
K
b
K
a
x 10
6
75 24 17.9
120 49 21.9 0.135
160 71 19.1 0.0731
200 93 15 16.1 0.0804
240 116 12.4 0.0502 880
280 138 10.2 0.0348
300 149 7.80 300
320 160 7.37 0.0500
360 182 5.18 0.0467
400 204 2.83 3.42 0.0502 42.0
440 227 2.19 0.0320
480 249 1.13 1.30 0.0305 10.0
520 271 0.84 0.0234
540 282 0.43
560 293 0.35 2.00
(a), Data from W.L. Marshall and E. V. Jones, " Reactor Chemistry Division Annual Progress
Report For Period Ending Jan. 31, 1965", ORNL-3789, p. 148, Oak Ridge National Laboratory;
also Phys. Chem. 70, 12 (December 1966).
Temperature





40


Figure 3.3. Dissociation constants K
B
, for NH
4
OH and LiOH (Cohen 1980).


Fig. 3.4

The calculated pH at high temperature of pure water, dilute solutions of ammonia, and strong base, are plotted in Fig. 3.4, where SB is
molal concentration of added base.
In Fig. 3.4, the point for K2SO4, at 560 F, indicates that a 0.5 x 10
-4
M solution of K2SO4 is more alkaline at that temperature than a solution of
NH3 which as a pH at 75F of 10.0 (11.1 ppm NH3).



7-Acid and Base_S11
41


Figure 3.4. pH of solutions of strong base (SB), NH3, and pure water (Cohen 1980).


The dissociation equilibria are calculated from the following equations:

Dissociation of base:
[ ][ ]
[ ]
Ka
M OH
MOH
=
+
(3.18)
Dissociation of water:

[ ][ ]
K H OH
w
=
+
(3.16)
Mass balance for base:

[ ]
[ ] [ ]
M MOH B
+
+ = (3.17)
Charge balance (Condition of electroneutrality):


[ ] [ ] [ ]
M H OH
+ +
+ = (3.15)

For univalent weak bases,


[ ]
[ ]
[ ]
[ ]
B
K
H
H
K
K H
w w
B
=
|
\

|
|
|
+
|
\

|
|
|
+
+
+
1 (3.19)





42

Salts

- When an acid reacts with a base, the positive ions from the base and negative ions from the acid form an ionic compound called a salt,
such as NaCl.

- Salt is an ionic compounds that forms when a metal atom or a positive radical replaces the hydrogen of an acid.

(Benjamin, p 7)

- Some ions are so stable when surrounded by water molecules that, upon contact with water, they are very likely break off of any compound
they are associated with and become surrounded by water molecules, and are then very unlikely to participate in any subsequent reactions. Such
compounds are called salts.

Examples are sodium (Na
+
) and chloride (Cl
-
). Compounds of the form NaaX(s) or Z Cl b (s) tend to dissociate completely to Na plus X
a-
or Z
b+
plus
Cl
-
, respectively, whenever they are exposed to water.

NaaX a Na
+
+ X
a-


Z Cl b Z
b+
+ bCl
-


The X
a-
and Z
b+
ions might react with other dissolved species, but Na
+
and Cl
-
rarely do.


- A salt is a compound which dissociates in solution to form positive ions other than the hydrogen or hydronium ions and negative ions other
than the hydroxyl ion.

- e.g., sodium chloride, NaCl, dissociates to form sodium ions and chloride ions according to the following equation:

NaCl Na
+
+ Cl
-



- the reaction between a salt and water to form a weakly acidic or weakly basic solution.
- For example,
o The salt NaCl is said to be derived from HCl and NaOH.
o The sodium carbonate Na2CO3 is said to be derived from carbonic acid H2CO3 and NaOH.

- The strength of the acids and bases from which a salt is derived determines whether the solution of the salt is acidic or basic.

- Fig. 1-10 illustrates the relationships among acids and bases.

- For example,
o A salt derived from a strong acid and a strong base will not undergo hydrolysis. Its solution will be neutral.
e.g., NaCl.

o A salt derived from a strong acid and a weak acid and a weak base will undergo hydrolysis. Its solution will be acidic.
e.g., Ammonium chloride NH4Cl

o A salt derived from a weak acid and a strong base will undergo hydrolysis. Its solution will be basic.
e.g., Sodium carbonate, Na2CO3

o A salt derived from a weak acid and a weak base will undergo hydrolysis. Its solution can be acidic or basic, depending on the relative
strength of the acid and base from which it is derived.
e.g., Ammonium carbonate, (NH4)2 CO3 forms a basic solution.



High Volatility Materials (Cohen, p. 68)

3-5.1.1 NH3

Because of its volatility, NH3 is attractive as a source of alkalinity in reactor and boiler technology.

In a simple (single-stage) evaporation process the limiting concentration ratio will not exceed the reciprocal of the distribution constant, vapor to
liquid.

NH3 is quite stable, thermally, at the temperature of concern in reactor technology, but is subject to radiolysis.

Morpholine and cyclohexylamine are also used in conventional boiler technology as a source of basicity in the condensing portion of the steam
cycle.

The equilibrium is between un-ionized ammonia in the liquid and NH3 in the vapor.

[NH3]l [NH3]v (3.25)
7-Acid and Base_S11
43

[ ]
[ ]
K
NH
NH
D
v
l
=
3
3


Subscripts l and v denote the liquid and vapor phase, respectively.

--------------------------------
write [NH4
+
] = NH3 and
[NH4OH] = (1 ) NH3

[NH4
+
]
= ----------
NH3

[NH4OH]
1 = -------------
NH3

Mass balance: CT, NH3 = NH3 = [NH4OH] + [NH4
+
]

[NH4OH] = NH3 [NH4
+
] = NH3 NH3 = (1 ) NH3

--------------------------------

(Cohen 1980) - derived by Sato

Equilibrium Reactions:

NH4OH NH4
+
+ OH

NH4
+
NH3 + H
+


NH3 + H2O NH4
+
+ OH

H2O H
+
+ OH



Equilibrium Equations:

[ ][ ]
[ ]
K
NH OH
NH
b
=
+
4
3
(1)

[ ][ ]
Kw H OH =
+
(2)

[ ]
[ ]
[ ]
K
H NH
NH
a
=
+
+
3
4
not used

Mass balance:
CT, NH3 = NH3 = [NH3] + [NH4
+
] (3)

Charge balance:
[NH4
+
] + [H
+
] = [OH
-
] (4)

From mass balance(3),
[NH4OH] = CT, NH3 = [NH4
+
] (3)

From charge balance (4),
[OH
-
] = [NH4
+
] + [H
+
] (4)

Substituting (3) and (4) into (1) yields

44
[ ] [ ]
[ ]
[ ] [ ] [ ] { }
[ ]
K
NH OH
NH
NH NH H
C NH
b
T
NH
= =
+

+ + + +
+
4
3
4 4
4
3
,

[ ]
[ ] [ ]
1
3
4 4
4
4 4
K
b
NH
NH NH H
NH
NH NH H
=

+ +
+
+

+
+ +
+
+

(
|
\

(
|
\

|


Let = [NH4
+
] / NH3 =

[ ]
1
1
4
1
4
1
1
1
K
b
NH H NH H
K
b
OH OH
=
+
+
+

+
+
+

(
|
\

|
=

(
|
\

(
|
\

(
|
\

1
1
1
OH
K
OH
OH K
K OH
b
b
b

= +

(
|
\

|
=

(
+

(


OH
K OH
OH K
b
b

(
+

(


=

(
+
K
OH K
b
b


[ ]
1 1
1
1
1
1
=

(
+
=

(
+

(
+
=

(
+
=
+

(
=
+
+

K
OH K
OH K K
OH K
OH
OH K
K
OH
K
K H
b
b
b b
b
b
b b
w
/


[ ]
1
1
1
=
+
+

K
b
H
K
w



7-Acid and Base_S11
45
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
1
1
1
1
1
4
4
1
1
4
4
4
4 4
=
+
+

(
=
+
+

(
+

(
+

(
=
+
+
=
+
+

K
b
H
K
w
NH OH
NH OH
H
H OH
NH
NH OH
NH OH
NH OH NH


[ ]
1
4
3
=

NH OH
NH


or

[ ] [ ]
[ ]
[ ]
[ ]
[ ] [ ]
[ ]
[ ]
[ ]
[ ]
[ ]
1 1
4
1
4
4 4
4 4 4
4 4
4
4 4
3
=
+
=
+
+
+
=
+
+

+
+
+
=
+
+

NH
NH
NH
NH OH NH
NH OH NH NH
NH OH NH
NH OH
NH OH NH


[ ]
1
4
3
=

NH OH
NH


----------------------

The relationship is

[ ]
1
1
1
=
+
+

K
K
H
B
W
(3.26)

where [H
+
] is obtained from Eqn (3.19)

Various values of are assumed from which NH3 is calculated, and a curve of vs NH3 constructed. KD is then given by

[ ]
( )
NH
NH
K
v
D
3
3
1
=

(3.27)

The apparent distribution coefficient is, therefore

[ ]
( )( )
NH
NH
K K
v
D D
3
3
1

= =
'


Figure 3.12 shows KD for NH3 as a function of temperature for water as saturation pressure.


Iodine (Cohen, 1980; p.69)