Homework

Fundamentals of
Analytical Chemistry

Chapter 9


20, 21, 25, 27, 29

Acids, Bases, and Buffers A

Chapter 9(b)

Definitions

Focus in

Acid





Aqueous Solutions

Releases H+ ions in water (Arrhenius)

Proton donor (Bronsted
(Bronsted Lowry)
ElectronElectron-pair acceptor (Lewis)
Characteristic cation for the solvent (solvent(solvent-system)

Base





Releases OH- in water (Arrhenius)

Proton acceptor (Bronsted
(Bronsted Lowry)
ElectronElectron-pair donor (Lewis)
Characteristic anion for the solvent (solvent(solvent-system)

All aqueous solutions have OH-




KW


[H+][OH-]

More correct is H3O+

We will assume H+ and H3O+ are equivalent

Even more correct H9O4+

Most common approach

= [H ][OH ] = 1.0 x 10

25OC)

(at 25 C)

Note that concentrations rather than activities

Should use activities, but = 1.0 x 10-7
Will ignore activity coefficients unless specifically
asked to use them in calculations!

Aqueous Solutions


10-14

Note H2O(l) is not part of the equilibrium

expression
Activity of solvents by definition equal to 1

to)

have H+ ions.

When [H+]

H2O(l)  H+ + OH2H2O(l)  H3O+ + OH-

ions

All aqueous solutions (are considered

Aqueous Solutions

For any aqueous solution

this course is water as a solvent

Most common reference will be Bronsted

Lowry definitions

If


= [OH-] = 1.0 x 10-7

Neutral
Neutral solution

[H+] > [OH-]

Acidic
[H+] > 10-7
[OH-] < 10-7

Basic
[H+] < 10-7
[OH-] > 10-7

Typical Values

pH

range for H+ and OH- are

from greater than 10 to less than 10-15

Concentration


Difference between 1
1 and $100 trillion.

Compress
Compress scale


(10-15)




pH = -log [H+]

Actually, pH = -log aH+

Compress scale, gives mostly positive values
Inverse relationship to [H+]
As [H+] increases, pH decreases

[[-15]

scale more palatable by changing

sign


using logarithms

Range is then log (10) [1] to log

Make

Working definition:

Since



Range is then -1 to 15

acid has been defined as [H+] > 10-7

Acidic pH has values less than 7

Basic values have pH greater than 7

Error in


measurement of [H+] 5%

Since pH log function, error is 0.02 pH units

[0.05 / ln 10] = 0.0217 = 0.02

Calculation of pH for a Solution

Must


first define the type of solution

Acid

And the last shall be first

first

None


Strong
Weak


Base

Solution will still be neutral

Note that the change in ionic strength d/n change
the activity from 1.0 x 10-7
Kw = aH+ * aOH-

Strong
Weak




of the Above

Nothing in the solution to cause the hydrogen

ion concentration to change (NaCl
(NaCl))
pH = 7.00

Buffer
Acid Salt
None of the Above

pH for Acids

If



the solution is an acid

Species is a proton donor
Different levels of donation
donation
All (strong acid)
Some (weak acid)

Strong acids




HCl,
HCl, HBr,
HBr, HI
HNO3, HClO3, HClO4
H2SO4

pH for Acids

Strong acids donate all protons


[H+] = CHA

What

is the pH for the following solutions

of HCl (a strong acid)





1.0 x 10-2
1.0 x 10-5
1.0 x 10-7
1.0 x 10-10

Special situation will discuss later

pH for Acids

HOW CAN WE ADD

AN ACID TO A
SOLUTION AND
MAKE THE
SOLUTION BASIC???

pH for Acids

Remember,

pH values greater than 7

mean that the solution is basic!

What happened?

pH for Acids

For ALL acidic solutions,

there are 2

sources of protons



pH for Acids

The acid
Water

As [H+]
approaches 10-7


When [H+]

is large, we can ignore

contribution from water.



Neutral
Neutral [H+] = 10-7
LeChatlier
LeChatliers Principle causes a shift away
from the production of H+ from the
autoionization of water

Equilibrium shift
decreases
[H+] from water
becomes more
significant.

What is the pH
for a solution that
is 1.0 x 10-7 M in
HCl?
HCl?

pH for Acids

When do

we have to account for addition

of hydrogen ion due to the dissociation of
water, and when can we safely ignore this
contribution?





When [H
[H+]calc < 3 x 10-7, must account for
water dissociation
Translates to a pH > 6.5
Most cases we can ignore!

[ ][ ]
[ ] [ ] + [H ]
Also, [H ]
= [OH ] = x
Then, 1.0 x10 = (1.0 x10 + x )( x )
K w = H + OH
But H + = H +

water

acid

water

14

x 2 + 1.0 x10 7 x 1.0 x10 14 = 0

x=

1.0 x10 7

(1.0 x10 )

7 2

4(1)( 1.0 x10 14 )

2(1)

x = 6.2 x10 8

[H ] = 1.0 x10
+

+ 0.62 x10 7 = 1.62 x10 7

pH = log(1.62 x10 7 ) = 6.79

pH for Acids

Weak acids

CANNOT assume complete dissociation!

For the weak acid HA  H+ + AEquilibrium constant for this dissociation is Ka

Ka = [H+][A-] / [HA]




Subscript a indicates an acid dissociation constant

Unfortunately, we know none of the equilibrium
concentrations
Must relate analytical concentration to equilibrium
concentration

pH for Acids

What do



Cation

we know?

Ka
CHA

balance equation

Since a solution must be electrically neutral,

the concentration or all of the positive charges
must equal the concentration of all of the
negative charges

What

H+

Anions

Charge


pH for Acids

A-, OH Always have hydroxide ions in an aqueous

solution

Using the


Remember, that as [H+] increases, [OH-]

decreases

ions do we have in solution?

pH for Acids


pH for Acids

We can assume that [A-] >> [OH-]

Reduced our expression from 3

Therefore, [A-] + [OH-] [A-]



Substituting, [H+] [A-]

(1)

True when [H+] > 3 x 10-7

Will be true for all weak acids we work with!

the equilibrium
constant expression

Ka = [H+] [H+] / [HA]

Ka = [H+]2 / [HA]

variables

to 2!

Mass balance equation

Substituting (1) into



charge balance equation

[H+] = [A-] + [OH-]




The analytical concentration for a species that

dissociates is equal to the sum of the
concentration of it
its identifiable pieces
For HA, CHA = [HA] + [A-]
Rearranging, [HA] = CHA [A-]
Substituting (1), [HA] = CHA [H+]
(2)

pH for Acids

pH for Acids

[ ]
[ ]
* (C [H ]) = [H ]
+ 2

Substituting (1) and

(2) into the
equilibrium
expression



Ka = [H+]2 / CHA [H+]

One equation, one
variable

Ka =
Ka

H
C HA H +

+ 2

Works for all situations we

HA

rearranging ;

[H ] = K C K [H ]
[H ] + K [H ] K C = 0
Quadratic in [H ]
+ 2

HA

+ 2

HA

[H ] = K

[H ] = K

K a2 4 * ( K a C HA )
2

will encounter,

but
but
What if CHA >> [H+]
Then CHA - [H+] CHA
Ka = [H+]2 / CHA
Rearranging [H+]2 = KaCHA
H + = K a CHA

[ ]

+ K a2 + 4 K a C HA
2

pH for Acids

Limitations for short
short equation


CHA >> [H+]

Method 1

pH for Acids

Method



Do the problem the short way, test the assumption,

and redo the problem if assumption is wrong.


Assumption will be valid if relative error < 5%

If 100*Ka < CHA, the assumption will introduce
less than 5% error
First test, is 100*Ka < CHA
YES, then you can use the short
short equation
NO, then use the quadric based equation
NOT SURE, then use the quadratic based
equation

Method 2
ALWAYS use the quadratic based equation
(safest)

Will always work

pH for Bases

What


changes for bases?

[OH-] > [H+]

Calculate [OH-]
Must convert to pH somehow

Method




pH for Bases

Method





[H+] * [OH-] = 1.0 x 10-14

[H+] = 1.0 x 10-14 / [OH-]
pH = -log [H+]




pH for Bases

Strong bases


Soluble hydroxides
Group I hydroxides
Ba2+, Sr2+

Soluble oxides
Group I oxides




M2O  2M + + O2O2- + H2O  2OH[OH-] = 2*CSALT

[H+] * [OH-] = 1.0 x 10-14

log ([H+] * [OH-]) = log (1.0 x 10-14)
-log ([H+] * [OH-]) = -log (1.0 x 10-14)
-log [H+] + -log [OH-] = 14.00
pH + pOH = 14.00
14.00 pOH = pH

pH for Bases

Strong base



we know [OH-]

Calculate pH using Method 1 or 2

Ignore contribution due to dissociation of
water unless:

[OH-]calc < 3 x 10-7

pHcalc < 7.5
Mirrors
Mirrors strong acid rules.

Others which are of no analytical importance

pH for Bases

Weak bases

We can

B + H2O  HB+ + OHKb = [HB+][OH-] / [B]




[OH-]

for weak bases

[OH ] = K

pH for Bases
use the second equation only
when CB > 100Kb



Similar to situation with weak acids

When in doubt, use the quadratic form

+ K b2 + 4 K bC B
2

OR

[OH ] =

K bC B

Conjugate Acid/Base Pairs

A

conjugate acid/base pair is a pair of

chemical species that differ by the
presence/absence of one proton (H+.) The
conjugate acid has one more proton than
the conjugate base.



HA / AHB+ / B

Do

not confuse conjugate base (or acid)

with base (or acid).
acid).

Conjugate Acid/Base Pairs

Conjugate

base of a strong acid IS NOT

basic!


Donates protons completely doesn

doesnt want
any
any back

Conjugate


base of a weak acid IS basic

Will take
take protons from water
Not really, but easier to picture

Conjugate


acid of a weak base IS acidic

Will donate protons

pH for Weak Bases

Appendix 3


Ka values only
Acetic acid (HC2H3O2)
Ammonium ion (NH4+)

How do we get Kb for a weak base?

What is the relationship between Ka and Kb for a
conjugate acid/base pair?

For HA H + + A ; K a =

[ H + ][ A ]
[ HA]

For A + H 2O HA + OH ; K b =
K a * Kb =

[ HA][OH ]
[ A ]

[ H + ][ A ] [ HA][OH ]
*
[ HA]
[ A ]

K a * K b = [ H + ][OH ] = K w = 1.0 x10 14

for conjugate acid / base pairs :
Kb =

K w 1.0 x10 14
=
Ka
Ka

Misc.

Buffers

Water is a leveling solvent

solvent


Two

Strongest acid in water is H3O+

Acids stronger than H3O+ transfer protons

completely to water to form the hydronium ion.
Relative to acidic strength, all strong acids are the
same strength


Strongest base in water is OH Bases stronger than OH- react completely with
water to form the hydroxide ion (O2-)

properties

Resistant to pH upon the addition of a small

amount of strong acid/base
Maintain pH upon dilution

Mixture

of a (significant amount of a) weak

conjugate acid/base pair



HC2H3O2/C2H3O2NH4+/NH3

Buffers

Resistant



to pH

Assume [ HA] = C HA ; [ A ] = C A

Strong acid reacts with the base

Strong base reacts with the acid

Maintains pH upon


Buffers
[ H + ][ A ]
Ka =
[ HA]

Then K a = [ H + ]

C A
C HA

log K a = log [ H + ] A
C HA

C
log K a = log [ H + ] + log A
C HA
rearranging :

dilution

pH of a buffer is controlled by the ratio of the

weak acid to the weak base

C
log [ H + ] = log K a + log A
C HA
This is the Henderson Hasselbalch equation

Buffers

What if CHA [HA]



Strong
Strong weak acid
Dissociation of acid
causes CHA > [HA]

Buffers

Use when Ka10-3

Analagous equation
for strong
strong weak
bases


Will not derive (or use)

From the Henderson Hasselbalch equation :

[H + ] = Ka

What


C HA [ H ]
C A + [ H + ]

[ H ] * (C A + [ H + ]) = K a * (C HA [ H + ])
[ H + ]2 + C A [ H + ] = K a C HA K a [ H + ]

Maximum pH = pKa + log (10) = pKa + 1

Minimum pH = pKa + log (0.1) = pKa 1

rearranging :
+ 2

[ H ] + C A [ H ] + K a [ H ] K aC HA = 0
[ H + ]2 + (C A + K a )[ H + ] K a C HA = 0
+

[H ] =

is a significant concentration
concentration

For a buffer, the ratio of base to acid must be

between 0.1 and 10
Using these limits

For a buffer, pH = pKa 1

(C A + K a ) + (C A + K a ) 2 + 4 K aC HA
2

Buffers

Buffer capacity (
()


Moles of a strong acid or a strong base that

causes 1.00 L of the buffer to undergo a 1.00
unit change in pH
Function of concentration of components and
also the ratio of the components
Best
Best buffer when ratio of base to acid is 1
pH = pKa + log (1)
pH = pKa gives the ideal
ideal buffer

Preparing Buffers

Mix

weak acid and a soluble salt of the

conjugate base


HC2H3O2 + NaC2H3O2

Mix

weak base and a soluble salt of the

conjugate acid


NH3 + NH4Cl

Partial neutralization


HC2H3O2 + NaOH when NaOH is the limiting

reactant
NH3 + HCl when HCl is the limiting reactant