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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 1.0x10-8M solution of
MHCl?
HCl = 1.0 x 10
-8 M

[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!
It’s [H
BACK
+] ! Systematic Equilibrium
total = [H ]water + [H ]HCl
+ +

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 ?

01 X 10-14 at 25oC [H+]total[OH-] = 1.01 X 10-14 ([H+]water + 1.01 X 10-14 ( x + 1.01 X 10-14 .0 x 10-8 M) [OH-] = 1.0 x 10-8M) x = 1.0 x 10-8M let [H+]water = x = [OH-] Kw = [H+]total[OH-] = 1.[H+]total = [H+]water + [H+]HCl [H+]total = [H+]water + 1.

0 x 10-8M) x = 1.( x + 1.5 x 10-8M = 1.05 x 10-7M pH = 6.51 x 10-8M [H+]total = 9.0 x 10-8M [H+]total = 10.01 X 10-14M2 by quadratic x = 9.98 .51 x 10-8M + 1.

50 .1 x 10-4 [HF] HF (aq) H+ (aq) + F.1 x 10-4 Ka << 1 0.55 x 10-4 0.50 0.019 M pH = -log [H+] = 1.72 [HF] = 0.50 0.50 – x = 0.50 x = 0.1 x 10-4 x2 = 3.x x x x2 Ka = = 7.x x2 Ka  = 7.(aq) Initial (M) 0. What is the pH of a 0.019 M [H+] = [F-] = 0.48 M .00 0.00 Change (M) -x +x +x Equilibrium (M) 0.5 M HF solution (at 250C)? - [H + ][F ] HF (aq) - H (aq) + F (aq) + Ka = = 7.50 .50 – x  0.

50 – x  0.05 More than 5% 0.50 When x is less than 5% of the value from which it is subtracted.8% 0.05 M Approximation not ok.006 M x 100% = 12% 0. What is the pH of a 0.1 x 10-4 x = 0. Must solve for x exactly using quadratic equation or method of successive approximation.006 M 0. 0.05 M HF solution (at 250C)? x2 Ka  = 7.019 M Less than 5% x = 0. .019 x 100% = 3. When can I use the approximation? Ka << 1 0.50 M Approximation ok.

122 0.7 x 10-4 Ka << 1 0.(aq) Initial (M) 0.x x x x2 Ka = = 5.7 x 10-4? HA (aq) H+ (aq) + A.95 x 10-5 x = 0.00 0.122 M Approximation not ok.x x2 Ka  = 5.00 Change (M) -x +x +x Equilibrium (M) 0.8% 0. .122 M monoprotic acid whose Ka is 5.122 – x  0.122 .122 0.0083 M 0. What is the pH of a 0.122 .7 x 10-4 x2 = 6.0083 M More than 5% x 100% = 6.122 0.

0081 x = .x x x [H+] = x = 0.7 x 10-4 x2 + 0.95 x 10-5 = 0 0.122 .00 Change (M) -x +x +x Equilibrium (M) 0.122 .122 0.0081 HA (aq) H+ (aq) + A. x2 Ka = = 5.09 .x -b ±  b2 – 4ac ax2 + bx + c =0 x= 2a x = 0.00057x – 6.0081 M pH = -log[H+] = 2.(aq) Initial (M) 0.0.00 0.

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 .

(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+]. .Weak Bases and Base Ionization Constants NH3 (aq) + H2O (l) NH4+ (aq) + OH.

Prushan .CHM 112 Summer 2007 M.

(aq) Kw KaKb = Kw Weak Acid and Its Conjugate Base Kw Kw Ka = Kb = Kb Ka 15.(aq) + H2O (l) OH.(aq) + HA (aq) Kb H2O (l) H+ (aq) + OH.7 .Ionization Constants of Conjugate Acid-Base Pairs HA (aq) H+ (aq) + A.(aq) Ka A.

The degree of ionization in aqueous solution depends on the formal concentration of HOAc. or completely ionized in the solvent. as well as the existence of other acid or base species that may be in solution. Acetic acid is a relatively weak acid. Fractional Ionization of a Monoprotic Weak Acid Weak acids are those that are not leveled. .

and use the definition of formal Which is a mathematical statement of mass balance.e.. .If we divide both sides by volume. the sum of the molar concentrations of all acetic species equals the formula weights we put into solution. i.

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 &   The ratios are often called the "alpha“ (a) of acetate and acetic acid respectively. .

Fractional Composition  plot for acetic acid What is the pH when [HA] = [A-]??? 1  A ( pH )  HA( pH) 0. .5 4.75 0 0 2 4 6 8 10 12 pH Which is the pKa….

CH3COONa (s) Na+ (aq) + CH3COO.(aq) common ion CH3COOH (aq) H+ (aq) + CH3COO. The presence of a common ion suppresses the ionization of a weak acid or a weak base.(aq) . Consider mixture of CH3COONa (strong electrolyte) and CH3COOH (weak acid).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.

pH = pKa + log -log [H ] = -log Ka + log + [A ] [acid] [HA] - pH = pKa + log [A ] pKa = -log Ka [HA] .(aq) [HA] Ka [HA] [H ] = + [A-] Henderson-Hasselbalch equation [HA] -log [H+] = -log Ka . NaA (s) Na+ (aq) + A. Consider mixture of salt NaA and weak acid HA.log [A-] [conjugate base] .(aq) [H+][A-] Ka = HA (aq) H+ (aq) + A.

52 M HCOOK? Mixture of weak acid and conjugate base! HCOOH (aq) H+ (aq) + HCOO.52 + x  0.77 .30] HCOOH pKa = 3.x x 0.30 M HCOOH and 0.(aq) Initial (M) 0.52 + x - Common ion effect pH = pKa + log [HCOO ] [HCOOH] 0.01 [0.30 .30 [0.30 – x  0.77 + log = 4.52] 0. What is the pH of a solution containing 0.52 pH = 3.52 Change (M) -x +x +x Equilibrium (M) 0.30 0.00 0.

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) + H2O (l) . A weak acid or a weak base and 2.A buffer solution is a solution of: 1.(aq) + CH3COOH (aq) CH3COO.

is a weak base and HCO3. (c) Na2CO3/NaHCO3 (a) HF is a weak acid and F. Which of the following are buffer systems? (a) KF/HF (b) KBr/HBr.is it conjugate acid buffer solution .is its conjugate base buffer solution (b) HBr is a strong acid not a buffer solution (c) CO32.

0 mL of the buffer solution? NH4+ (aq) H+ (aq) + NH3 (aq) [NH3] [0.10 0.20 .028 0.001 0.28] = 9.025 [0.25] [NH4 ] = + [NH3] = pH = 9.0 mL of 0.25 + log 0.025 final volume = 80.10 [0.0 0.25 pH = 9.30] pH = pKa + log pKa = 9.0 mL + 20.029 0.(aq) H2O (l) + NH3 (aq) end (moles) 0.36 M NH4Cl buffer system.36] start (moles) 0.25 + log = 9.0 mL = 100 mL 0.024 NH4+ (aq) + OH.050 M NaOH to 80.30 M NH3/0.17 [NH4+] [0.028 0. What is the pH after the addition of 20. Calculate the pH of the 0.

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 A buffered solution resists changes in pH when acids and bases are added or when dilution occurs.

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  plots .

the fluid within the cell and the fluids surrounding the cells have a characteristic and nearly constant pH. and one of the most important is through buffer systems. . This pH is maintained in a number of ways. •      In all multicellular organisms. and whether these groups are charged or neutral has a significant effect on the biological activity of the molecule. 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. Two important biological buffer systems are the dihydrogen phosphate system and the carbonic acid system.

and the equilibrium shifts to the left. • H2PO4-(aq) H+(aq) + HPO42-(aq) Ka = [H +] [HPO42-] =6. they react with H2PO4-. This buffer system consists of dihydrogen phosphate ions (H2PO4-) as hydrogen-ion donor (acid) and hydrogen phosphate ions (HPO42-) as hydrogen-ion acceptor (base). The phosphate buffer system •      The phosphate buffer system operates in the internal fluid of all cells. they are consumed in the reaction with HPO42-. .23 × 10-8 at 25oC [H2PO4-] • If additional hydrogen ions enter the cellular fluid. If additional hydroxide ions enter the cellular fluid. and shifting the equilibrium to the right. producing HPO42-.

21 Buffer solutions are most effective at maintaining a pH near the value of the pKa.9 to 7. cellular fluid has a pH in the range 6. and the phosphate buffer is effective in maintaining this pH range. . In mammals.are the same.and HPO42.when the concentrations of H2PO4. what will the pH equal? 7.4.

the condition is called alkalosis. the concentration of hydrogen carbonate ion is about twenty times the concentration of carbonic acid. In blood plasma. the carbonic acid and hydrogen carbonate ion equilibrium buffers the pH. The pH of arterial blood plasma is 7. If the pH falls below this normal value. In this buffer. If the pH rises above the normal value.and additional OH. H2CO3(aq) H+(aq) + HCO3-(aq) Additional H+ is consumed by HCO3. and the pKa is 6. carbonic acid (H2CO3) is the hydrogen-ion donor (acid) and hydrogen carbonate ion (HCO3-) is the hydrogen-ion acceptor (base). In blood plasma.9 × 10-7.is consumed by H2CO3.1 at body temperature. a condition called acidosis is produced. .40. Ka for this equilibrium is 7. Carbonate Buffer Another biological fluid in which a buffer plays an important role in maintaining pH is blood plasma.

Carbonic acid concentration is controlled by respiration. In the lungs. Carbonic acid is in equilibrium with dissolved carbon dioxide gas. CO2(aq) CO2(g) . excess dissolved carbon dioxide is exhaled as carbon dioxide gas. The concentrations of hydrogen carbonate ions and of carbonic acid are controlled by two independent physiological systems. that is through the lungs. H2CO3(aq) CO2(aq) + H2O(l) An enzyme called carbonic anhydrase catalyzes the conversion of carbonic acid to dissolved carbon dioxide.

The concentration of hydrogen carbonate ions is controlled through the kidneys. Normal metabolism releases mainly acidic materials: carboxylic acids such as lactic acid (HLac). Excess hydrogen carbonate ions are excreted in the urine. H2CO3(aq) CO2(aq) + H2O(l) . 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. 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. These acids react with hydrogen carbonate ion and form carbonic acid.

Changes in carbonic acid concentration can be effected within seconds through increased or decreased respiration. and the excess carbon dioxide is released into the air in the lungs. The body maintains the buffer by eliminating either the acid (carbonic acid) or the base (hydrogen carbonate ions). Changes in hydrogen carbonate ion concentration. require hours through the relatively slow elimination through the kidneys . The carbonic acid-hydrogen carbonate ion buffer works throughout the body to maintain the pH of blood plasma close to 7.An increase in CO2(aq) concentration stimulates increased breathing.40. however.

EXAMPLE: What is the ratio of [H2CO3]/[HCO3-] in the blood buffered to a pH of 7.0 x 10-8M .4 x 10- 7 M [H3O+] = 10-pH = 10-7.4 = 4.40? Ka = 4.

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 .