ACIDS WITH LARGE VALUES OF Ka ARE STRONGER THAN ACIDS WITH SMALLER VALUES OF Ka Ka = 1.

74x10-5M

EXAMPLE 5: (a) Find pH of 0.0500M CH3COOH; (b) the concentrations of the species; and (c) % dissociation of acetic acid.

(a)
Init. Change Eqm. 0.05 -x 0.05-x 0 +x x 0 +x x

x2 = 1.74 x105 0.05 x

x 2 = 1.74 x105 ( 0.05 x )

Solve quadratic equation or use method of successive approximations

METHOD OF SUCCESSIVE APPROXIMATION

x 2 = 1.74 x105 ( 0.05 x )

x is small with respect to 0.05. First approximation, x = 0.

x 2 = 1.74 x105 ( 0.05 )

x = 9.33 x 10-4 M For small Ka this is sufficient.

x 2 = 1.74 x105 ( 0.05 9.33 x104 ) 2nd approximation,

x = 9.24 x 10-4 M

x 2 = 1.74 x105 ( 0.05 9.24 x104 ) 3rd approximation,

x = 9.24 x 10-4 M

SHORTCUT METHOD OF SUCCESSIVE APPROXIMATION

x 2 = 1.74 x105 ( 0.05 x )

0 ENTER

x = 1.74 x105 ( 0.05 x )

0 ENTER ENTER ENTER 9.33E-4 9.24E-4 9.24E-4

TI-83

(1.74E-5 (.05 ANS) )

[H3O+] = 9.24 x 10-4M pH = -log [H3O+] = -log(9.24E-4) = 3.03

Aside, log(9.33E-4) = 3.03

(b) (c)

[CH3COO-] = 9.24 x 10-4M [CH3COOH] = 0.05 -x = 0.05 - 9.24 x 10-4 = 0.0491M % CH3COOH dissociated = (x/[CH3COOH]0)(100%) = (9.24 x 10-4 /0.05)(100%) = 1.8%

% Dissociation of Acetic Acid as a Function of Its Initial Concentration

Technique of example 5 works for [CH3COOH]0 > 2x10-5M Why not for smaller concentrations?

x = 1.74 x105 ( 2.0 x105 x ) x1 = 1.9 x105 ; x = 1.18 x105 M

% CH3COOH dissociated = (x/[CH3COOH]0)(100%) = (1.18 x 10-5 /2x10-5)(100%) = 59 %
McQuarrie

pKa Defined pKa = -log Ka pKa = -log Ka = -log(1.74E-5) = 4.76 for acetic acid

McQuarrie

BASES WITH LARGE VALUES OF Kb ARE STRONGER THAN BASES WITH SMALLER VALUES OF Kb

McQuarrie

BASES WITH LARGE VALUES OF Kb ARE STRONGER THAN BASES WITH SMALLER VALUES OF Kb

All have the same reaction as NH3 (aq):

McQuarrie

McQuarrie

EXAMPLE 6: Calculate the pH and the concentrations of all the species in a 0.755 M hydroxylamine, HONH2(aq), solution.

Init. Change Eqm.

0.755M -x 0.755-x

0 +x x

0 +x x

x2 = 1.07 x108 0.755 x

x 2 = 1.07 x108 ( 0.755 x )

x = 1.07 x108 ( 0.755 0 ) = 8.99x10-5

pOH = -log [OH-]= -log(8.99E-5) = 4.05 pH = 14 - pOH =14 4.05 = 9.95 [HONH3+] = x = 8.99 x 10-5M [HONH2] = 0.755 x = 0.755 - 8.99 x 10-5 = 0.755M

THE PAIR OF SPECIES HB,B- IS CALLED A CONJUGATE ACID-BASE PAIR

HB ( aq ) + H 2O ( l )

H 3O + ( aq ) + B
Conjugate Base

Acid

Base

Conjugate Acid

McQuarrie

EXAMPLE 7: Determine the conjugate base for NH4+(aq).

Acid

Base

Conjugate Acid

Conjugate Base

SALTS OF THE CONJUGATE BASE OF STRONG ACIDS: ACIDIC, BASIC, OR NEUTRAL? NEUTRAL

HCl(g) +H2O(l) H3O+(aq) +Cl-(aq) Cl-(aq) +H2O(l) No Reaction

Dissociates completely

Cl-(aq) has no tendency to grab H+ from H2O

CATIONS OF STRONG BASES: ACIDIC, BASIC, OR NEUTRAL? NEUTRAL

NaOH(aq) Na+(aq) + OH-(aq) Dissociates completely Na+(aq) +H2O(l) No Reaction Na+(aq) has no tendency to grap OH- from H2O NaCl(aq) CaBr2(aq)

EXAMPLES

NEUTRAL NEUTRAL

SALTS OF THE CONJUGATE BASE OF WEAK ACIDS: ACIDIC, BASIC, OR NEUTRAL? BASIC

HCN(aq) +H2O(l)

H3O+(aq) +CN-(aq) Mostly undissociated HCN(aq) +OH-(aq) CN-(aq) can grab H+ from H2O CN-(aq) +H2O(l)

THE WEAKER THE ACID THE BETTER IT CAN GRAB H+ FROM H2O AND THE STRONGER THE BASE
SIMILARLY, SALTS OF THE CONJUGATE ACID OF WEAK BASES: ACIDIC

EXAMPLES

NaCN(aq) NH4Cl(aq) KI(aq)

BASIC

Ca(CH3COO)2(aq) BASIC
ACIDIC NEUTRAL

If this slide and the last one are confusing, see analogy for salts of weak acids using dogs and bones found in the Supplemental Material.

SALTS OF THE CONJUGATE BASE OF WEAK ACIDS ARE BASIC EXAMPLE 8: Determine the pH of 0.400M NaCH3COO (aq). Kb = ?

2 H 2O ( l ) H 3O + ( aq ) + OH ( aq )

Kw Kb =

Init. Change Eqm.

0.400M -x 0.4-x

0 +x x

0 +x x

1014 M 2 = 1.74 x105 M

= 5.75 x1010 M

x2 = 5.75 x1010 0.4 x

x 2 = 5.75 x1010 ( 0.4 x )

x = 5.75 x1010 ( 0.4 0 ) = 1.52 x105 M

pOH = -log [OH-]= -log(1.52E-5) = 4.82

pH = 14 - pOH =14 4.05 = 9.18

SIMILARLY, SALTS OF THE CONJUGATE ACID OF WEAK BASES ARE ACIDIC EXAMPLE 9: Determine the pH of 0.400M NH4Cl (aq). Ka = ?

SIMILARLY, SALTS OF THE CONJUGATE ACID OF WEAK BASES ARE ACIDIC EXAMPLE 9: Determine the pH of 0.400M NH4Cl (aq). Ka = ?

+ NH 4 ( aq ) + OH ( aq ) H 2O ( aq ) + NH 3 ( aq )

K1 = Kw

1 Kb

2 H 2O ( l ) H 3O + ( aq ) + OH ( aq )

Ka =

Kw Kb

SIMILARLY, SALTS OF THE CONJUGATE ACID OF WEAK BASES ARE ACIDIC EXAMPLE 9: Determine the pH of 0.400M NH4Cl (aq). Ka = ?

+ NH 4 ( aq ) + OH ( aq ) H 2O ( aq ) + NH 3 ( aq )

K1 = Kw

1 Kb

2 H 2O ( l ) H 3O + ( aq ) + OH ( aq )

Ka = Init. Change Eqm. 0.400M -x 0.4-x 0 +x x 0 +x x

Kw Kb

1014 M 2 = 1.75 x105 M = 5.71x1010 M

x2 = 5.71x1010 0.4 x

x = 1.51x105
pH = -log [H3O+] = -log(1.51E-5) = 4.82

For conjugate bases or acids: K a K b = K w

For the conjugate base:

Kb =

For the conjugate acid:

Ka =

Kw Kb

AQUEOUS SOLUTIONS OF MANY SALTS ARE EITHER ACIDIC OR BASIC (1)

HCl ( aq ) + H 2O ( l ) H 3O + ( aq ) + Cl ( aq ) NaOH ( aq ) Na + ( aq ) + OH ( aq )

K>>1

K>>1

Na+ and Cl- are neutral ions (pH does not change in their presence). Neutral cations are cations of strong bases. Neutral anions are anions of strong acids (except sulfuric acid). NaCl, KClO4, CsNO3 (2) The basic anions are the conjugate bases of weak acids. Because most acids are weak, most anions are basic. CH3COO-, F-, CO32(3) The acidic cations include the conjugate acids of weak bases. NH4+, CH3NH3+

AQUEOUS SOLUTIONS OF MANY SALTS ARE EITHER ACIDIC OR BASIC (4)

The acidic cations include the cations of some solvated metal ions.

McQuarrie

AQUEOUS SOLUTIONS OF MANY SALTS ARE EITHER ACIDIC OR BASIC (5)

The hydrogen sulfate ion and the dihydrogen phosphate ion are acidic anions because each undergoes a second acid-dissociation reaction:

EXAMPLE 10: Predict whether the following salts produce acidic, neutral, or basic solutions when dissolved in water: NaCl, NaCH3COO, NH4Cl, and NH4F.

McQuarrie

SUMMARY

McQuarrie

More practice problems:

HSO4Ca(ClO4)2 KCN Cs2SO4 AlCl3 KNO3 NaI KCCl3COO

Acidic Neutral Basic Basic Acidic Neutral Neutral Basic Acidic Acidic

NH

+ 4

Kw 1014 = = 5.71x1010 Ka = 5 K b 1.75 x10

NH4Br NH4HCOO

HCOO

Kw 1014 = = 5.61x1011 Kb = 4 K a 1.78 x10