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Acid-Base Equilibrium

(Monoprotic) Chapter 9

THE TRUTH, THE WHOLE TRUTH AND


NOTHING BUT THE TRUTH.
Strong Acids and Bases
pH + pOH = - log Kw = pKw =
14.00
for Kw = 1.0x10-14
pH + pOH = - log Kw = pKw =
13.996
for Kw = 1.01x10-14
at 25oC
EXAMPLE: What is the pH
of a 1.0x10-8 M solution of
HCl?
MHCl = 1.0 x 10 M
-8

[H+]HCl = 1.0 x 10-8 M


pH = 8.00
OH NO! WHAT
WRONG!!!!!!!! SHOULD WE DO !
HCl is an acid!
Acids have pH less than 7!
What's wrong?
We ignored the fact that water is also an
ACID!
[H+
] l = [H+
]water + [H+
]HCl
It’s BACK ! Systematic Equilibrium
tota

near pH 7, the contribution of [H+] from


water becomes the dominate source for
the [H+] in the solution
SO HOW DO WE SOLVE THIS ?
[H+]total = [H+]water + [H+]HCl

[H+]total = [H+]water + 1.0 x 10-8 M

let [H+]water = x = [OH-]

Kw = [H+]total [OH-] = 1.01 X 10-14 at 25oC


[H+]total [OH-] = 1.01 X 10-14

([H+]water + 1.0 x 10-8 M) [OH-]


=
1.01 X 10-14 ( x + 1.0 x 10-8 M) x = 1.01 X 10-14
( x + 1.0 x 10-8 M) x = 1.01 X 10-14 M2
by quadratic
x = 9.51 x 10-8 M

[H+]total = 9.51 x 10-8 M + 1.0 x 10-8 M


[H+]total = 10.5 x 10-8 M = 1.05 x 10-7 M
pH = 6.98
What is the pH of a 0.5 M HF solution (at 250C)?

-
[H +
][F ]
HF (aq) -
H (aq) + F (aq)
+ Ka = = 7.1 x 10-4
[HF]
HF (aq) H+ (aq) + F- (aq)
Initial (M) 0.50 0.00 0.00
Change (M) -x +x +x
Equilibrium (M) 0.50 - x x x
x2
Ka = = 7.1 x 10-4 Ka << 1 0.50 – x ≈ 0.50
0.50 - x
x2
Ka ≈ = 7.1 x 10-4 x2 = 3.55 x 10-4
0.50 x = 0.019 M
[H+] = [F-] = 0.019 M
pH = -log [H+] = 1.72
[HF] = 0.50 – x = 0.48 M
When can I use the approximation?
Ka << 1 0.50 – x ≈ 0.50

When x is less than 5% of the value from which it is subtracted.


0.019 M Less than 5%
x = 0.019 x 100% = 3.8%
0.50 M Approximation ok.
What is the pH of a 0.05 M HF solution (at 250C)?
x2
Ka ≈ = 7.1 x 10-4 x = 0.006 M
0.05
More than 5%
0.006 M
x 100% = 12% Approximation not ok.
0.05 M
Must solve for x exactly using quadratic equation or method
of successive approximation.
What is the pH of a 0.122 M monoprotic acid whose
Ka is 5.7 x 10-4 ?
HA (aq) H+ (aq) + A- (aq)
Initial (M) 0.122 0.00 0.00
Change (M) -x +x +x
Equilibrium (M) 0.122 - x x x
x2
Ka = = 5.7 x 10-4 Ka << 1 0.122 – x ≈ 0.122
0.122 - x
x2
Ka ≈ = 5.7 x 10-4 x2 = 6.95 x 10-5 x = 0.0083 M
0.122

0.0083 M More than 5%


x 100% = 6.8%
0.122 M Approximation not ok.
x2
Ka = = 5.7 x 10-4 x2 + 0.00057x – 6.95 x 10-5 = 0
0.122 - x
-b ± √b2 – 4ac
ax2 + bx + c =0 x=
2a
x = 0.0081 x = - 0.0081

HA (aq) H+ (aq) + A- (aq)


Initial (M) 0.122 0.00 0.00
Change (M) -x +x +x
Equilibrium (M) 0.122 - x x x

[H+] = x = 0.0081 M pH = -log[H+] = 2.09


Ionized acid concentration at equilibrium
percent ionization = x 100%
Initial concentration of acid

For a monoprotic acid HA

[H+]
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0
Weak Bases and Base Ionization Constants

NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

[NH4+][OH-]
Kb =
[NH3]

Kb is the base ionization constant

weak base
Kb
strength

Solve weak base problems like weak acids


except solve for [OH-] instead of [H+].
CHM 112 Summer 2007 M.
Prushan
Ionization Constants of Conjugate Acid-Base Pairs

HA (aq) H+ (aq) + A- (aq) Ka

A- (aq) + H2O (l) OH- (aq) + HA (aq) Kb

H2O (l) H+ (aq) + OH- (aq) Kw

KaKb = Kw

Weak Acid and Its Conjugate Base

Kw Kw
Ka = Kb =
Kb Ka

15.7
Fractional Ionization of a
Monoprotic Weak Acid

Weak acids are those that are not leveled,


or completely ionized in the solvent.

Acetic acid is a relatively weak acid. The


degree of ionization in aqueous solution
depends on the formal concentration of
HOAc, as well as the existence of other acid
or base species that may be in solution.
If we divide both sides by volume, and use the definition of formal

Which is a mathematical statement of mass balance, i.e., the sum of the


molar concentrations of all acetic species equals the formula weights we put
into solution.
A Little Algebra….

and substituted into the formal mass balance equation to yield

The fraction of acid in acetate form is


[OAc-]/FHOAc . Solving for this fraction
results in the amount of HOAc in the form
of the acetate

&
α α

The ratios are often called the "alpha“ (a) of acetate and acetic acid respectively.
Fractional Composition (α ) plot for acetic acid

What is the pH when [HA] = [A-]???


1

α A ( pH )

α HA ( pH )
0.5
4.75

0
0 2 4 6 8 10 12
pH

Which is the pKa….


The common ion effect is the shift in equilibrium caused by the
addition of a compound having an ion in common with the
dissolved substance.

The presence of a common ion suppresses


the ionization of a weak acid or a weak base.

Consider mixture of CH3COONa (strong electrolyte) and


CH3COOH (weak acid).
CH3COONa (s) Na+ (aq) + CH3COO- (aq)
common
ion
CH3COOH (aq) H+ (aq) + CH3COO- (aq)
Consider mixture of salt NaA and weak acid HA.

NaA (s) Na+ (aq) + A- (aq) [H+][A-]


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

Ka [HA]
[H ] =
+
[A-] Henderson-Hasselbalch
equation
[HA]
-log [H+] = -log Ka - log
[A-] [conjugate base]
- pH = pKa + log
-log [H ] = -log Ka + log
+ [A ] [acid]
[HA]
-
pH = pKa + log [A ] pKa = -log Ka
[HA]
What is the pH of a solution containing 0.30 M HCOOH
and 0.52 M HCOOK?

Mixture of weak acid and conjugate base!

HCOOH (aq) H+ (aq) + HCOO- (aq)


Initial (M) 0.30 0.00 0.52
Change (M) -x +x +x
Equilibrium (M) 0.30 - x x 0.52 + x
-
Common ion effect pH = pKa + log [HCOO ]
[HCOOH]
0.30 – x ≈ 0.30
[0.52]
0.52 + x ≈ 0.52 pH = 3.77 + log = 4.01
[0.30]
HCOOH pKa = 3.77
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!

A buffer solution has the ability to resist changes in pH upon


the addition of small amounts of either acid or base.

Consider an equal molar mixture of CH3COOH and CH3COONa

Add strong acid


H+ (aq) + CH3COO- (aq) CH3COOH (aq)
Add strong base
OH- (aq) + CH3COOH (aq) CH3COO- (aq) + H2O (l)
Which of the following are buffer systems? (a) KF/HF
(b) KBr/HBr, (c) Na2CO3/NaHCO3

(a) HF is a weak acid and F- is its conjugate base


buffer solution
(b) HBr is a strong acid
not a buffer solution
(c) CO32- is a weak base and HCO3- is it conjugate acid
buffer solution
Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer
system. What is the pH after the addition of 20.0 mL of
0.050 M NaOH to 80.0 mL of the buffer solution?

NH4+ (aq) H+ (aq) + NH3 (aq)

[NH3] [0.30]
pH = pKa + log pKa = 9.25 pH = 9.25 + log = 9.17
[NH4+] [0.36]

start (moles) 0.029 0.001 0.024


NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)
end (moles) 0.028 0.0 0.025

final volume = 80.0 mL + 20.0 mL = 100 mL


0.028 0.025 [0.25]
[NH4 ] =
+
[NH3] = pH = 9.25 + log
0.10 0.10 [0.28] = 9.20
Buffers
A buffered solution resists changes in pH
when acids and bases are added or when
dilution occurs.
definition - a buffer solution is composed of:
a weak-acid and its salt (conjugate base)
or a weak-base and its salt (conjugate acid)
Buffers
Henderson-Hasselbalch Equation

[H3O+] = Ka ([HA]/[A-])
pH = pKa + log([A-]/[HA])

when the [A-] = [HA]


pH = pKa

AH HA! REMEMBER THE RESULT


FROM THE α plots
Biological Buffers
• Biochemical reactions are especially sensitive to pH. Most
biological molecules contain groups of atoms that may be charged
or neutral depending on pH, and whether these groups are
charged or neutral has a significant effect on the biological activity
of the molecule.

•      In all multicellular organisms, the fluid within the cell and the
fluids surrounding the cells have a characteristic and nearly
constant pH. This pH is maintained in a number of ways, and one
of the most important is through buffer systems.

Two important biological buffer systems are the dihydrogen


phosphate system and the carbonic acid system.
The phosphate buffer
system
•      The phosphate buffer system operates in the internal fluid of all
cells. This buffer system consists of dihydrogen phosphate ions
(H2PO4-) as hydrogen-ion donor (acid) and hydrogen phosphate ions
(HPO42-) as hydrogen-ion acceptor (base).

• H2PO4-(aq) H+(aq) + HPO42- (aq)

Ka = [H +] [HPO42- ] =6.23 × 10-8 at 25oC


[H2PO4-]

• If additional hydrogen ions enter the cellular fluid, they are consumed
in the reaction with HPO42- , and the equilibrium shifts to the left. If
additional hydroxide ions enter the cellular fluid, they react with
H2PO4-, producing HPO42-, and shifting the equilibrium to the right.
when the concentrations of H2PO4- and HPO42- are the same,
what will the pH equal?

7.21

Buffer solutions are most effective at maintaining a pH near


the value of the pKa. In mammals, cellular fluid has a pH in
the range 6.9 to 7.4, and the phosphate buffer is effective in
maintaining this pH range.
Carbonate Buffer
Another biological fluid in which a buffer plays an important role in maintaining
pH is blood plasma. In blood plasma, the carbonic acid and hydrogen carbonate
ion equilibrium buffers the pH.

In this buffer, carbonic acid (H2CO3) is the hydrogen-ion donor (acid) and hydrogen
carbonate ion (HCO3-) is the hydrogen-ion acceptor (base).

H2CO3(aq) H+(aq) + HCO3-(aq)


Additional H+ is consumed by HCO3- and additional OH- is consumed by
H2CO3. Ka for this equilibrium is 7.9 × 10-7 , and the pKa is 6.1 at body
temperature. In blood plasma, the concentration of hydrogen carbonate
ion is about twenty times the concentration of carbonic acid. The pH of
arterial blood plasma is 7.40. If the pH falls below this normal value, a
condition called acidosis is produced. If the pH rises above the normal
value, the condition is called alkalosis.
The concentrations of hydrogen carbonate ions and
of carbonic acid are controlled by two independent
physiological systems. Carbonic acid concentration is
controlled by respiration, that is through the lungs.
Carbonic acid is in equilibrium with dissolved carbon
dioxide gas.

H2CO3(aq) CO2(aq) + H2O(l)

An enzyme called carbonic anhydrase catalyzes the


conversion of carbonic acid to dissolved carbon
dioxide. In the lungs, excess dissolved carbon dioxide
is exhaled as carbon dioxide gas.

CO2(aq) CO2(g)
The concentration of hydrogen carbonate ions is
controlled through the kidneys. Excess hydrogen
carbonate ions are excreted in the urine.

The much higher concentration of hydrogen carbonate


ion over that of carbonic acid in blood plasma allows
the buffer to respond effectively to the most common
materials that are released into the blood. Normal
metabolism releases mainly acidic materials: carboxylic
acids such as lactic acid (HLac). These acids react with
hydrogen carbonate ion and form carbonic acid.

HLac(aq) + HCO3-(aq) Lac-(aq) + H2CO3(aq)

The carbonic acid is converted through the action of the


enzyme carbonic anhydrase into aqueous carbon
dioxide.
H2CO3(aq) CO2(aq) + H2O(l)
An increase in CO2(aq) concentration stimulates increased breathing, and the
excess carbon dioxide is released into the air in the lungs.

The carbonic acid-hydrogen carbonate ion buffer works throughout the body to
maintain the pH of blood plasma close to 7.40. The body maintains the buffer by
eliminating either the acid (carbonic acid) or the base (hydrogen carbonate ions).
Changes in carbonic acid concentration can be effected within seconds through
increased or decreased respiration. Changes in hydrogen carbonate ion
concentration, however, require hours through the relatively slow elimination
through the kidneys
EXAMPLE: What is the ratio of [H2CO3]/[HCO3-]
in the

blood buffered to a pH of 7.40? Ka = 4.4 x 10-


7
M

[H3O+] = 10-pH = 10-7.4 = 4.0 x 10-8 M


Buffer Capacity
• refers to the ability of the buffer to
retard changes in pH when small
amounts of acid or base are added
• the ratio of [A-]/[HA] determines the
pH of the buffer whereas the
magnitude of [A-] and [HA] determine
the buffer capacity