pH

 and  Buffers  
 Strengths of Acids and Bases
•  “Strength” refers to how much an acid or
base ionizes in a solution.

STRONG WEAK

Ionize completely (~100%) Ionize partially (usually

<10%)
Example: Example:
HClà H+ + Cl- HF H+ + F-
NaOH à Na+ + OH- NH3 + H2O NH4+ + OH-
Relative Dissociation of Acids
Ka  =  [H+]  [A-­‐]  ,    therefore  larger  Ka  values  indicate  stronger  acids.  
                     [HA]  
 Acids  and  Bases  
•  Strong  acid:  an  acid  that  is  completely  ionized  
in  aqueous  soluDon  
–  HCl,  HBr,  HI,  HNO3,  HClO4,  and  H2SO4  

Strong Acids are strong electrolytes

HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq)
H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)
 Acids  and  Bases  
•  Strong  base:  a  base  that  is  completely  ionized  
in  aqueous  soluDon  
–  LiOH,  NaOH,  KOH,  Ca(OH)2,  and  Ba(OH)2  
Strong Bases are strong electrolytes
H 2O
NaOH (s) Na+ (aq) + OH- (aq)
H 2O
KOH (s) K+ (aq) + OH- (aq)
H 2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
 Weak  Acids  and  Bases  
•  An  acid  or  base  that  is  incompletely  ionized  in  
aqueous  soluDon  
–  carboxylic  acids,  such  as  aceDc  acid,  are  weak  
acids  
conjugate acid-base pair
O O
+
CH 3 COH + H2 O CH 3 CO - + H3 O
Acid Base Conjugate base Conjugate acid
of acetic acid of water

conjugate acid-base pair

 Equilibrium  Constants      
for  Weak  Acids  

Weak  acid  has  Ka  <  1    

Leads  to  small  [H3O+]  and  a  pH  of  2  -­‐  7    
 Ionization Constants for Acids/Bases  

Acids Conjugate
Bases
Increase  
strength  

Increase  
strength  
 Ion Product of Water (Kw)
•  In  pure  liquid  water,  [H2O]  
•  water  autoprotolysis  constant     is  a  constant  value.    
•  water  autoionizaDon  constant     •  To  demonstrate  this,  
consider  1000  mL  of  water  
- + with  a  density  of  1.00  g/
H2 O OH + H
mL.    
[H ][ OH ] •  This  1.00  liter  (1000  mL)  
+ - + -
[H ][ OH ]
Ka = = would  weigh  1000  grams.  
[H 2O] 55.5
•  This  mass  divided  by  the  
K w = K a x 55. 5 = [H + ][ OH - ] molecular  weight  of  water  
(18.0152  g/mol)  gives  55.5  
K w = 10 -14 moles.    
•  The  "molarity"  of  this  
water  would  then  be  55.5  
-
Kw = [H ][OH ] = 1.0 x 10
+ - 14
mol  ÷  1.00  liter  or  55.5  M.  
 The Ion Product of Water

At 250C Solution Is
[H+] = [OH-] neutral
Kw = [H+][OH-] = 1.0 x 10-14 [H+] > [OH-] acidic
For neutral solution: [H+] < [OH-] basic

[H+] = [OH-] = x

1.0 x 10-14 = x2

1.0 x 10-7 M = x = [H+] = [OH-]

 The pH Scale
Kw = [H+][OH-] = 1.0 x 10-14 Kw is the basis for pH scale.

pH = -log [H+] pH p = power

H = Hydrogen ion concentration

Solution Is At 250C
neutral [H+] = [OH-] [H+] = 1 x 10-7 pH = 7
acidic [H+] > [OH-] [H+] > 1 x 10-7 pH < 7
basic [H+] < [OH-] [H+] < 1 x 10-7 pH > 7

pH [H+]
•  In general for a number X,

− pX
p X = − log X X =10

pX = log X X = 10 pX
•  In general for a number X,
− pX
p X = − log X X =10
For example, pKw = -log Kw.
- −14
K w = [H ][OH ] = 1.0 ×10
+

(
pK w = − log [H ][OH ] = 14
+ -
)
-
pK w = − {log[ H ] + log[OH ]} = 14
+

pK w = − log[H + ] − log[OH - ] = 14
pK w = pH + pOH = 14
Calculations with pH and [H ]
+

pH = – log [H+]

What is pH if [H+] = 6.3 x 10–5? Ans: 4.2

[H+] = 10–pH

What is [H+] if pH = 7.4? Ans: 3.98 x 10–8 M

 pH or pOH of
strong acid or base
Complete dissociation

HCl (aq) à H+ + OH –
0.1 M 0.1 M 0.1 M
pH = -log [H+] = -log (0.1M) = 1
Kw = [H+][OH-] = 1.0 x 10-14

pKw = 14 = pH + pOH

pOH = 14 – 1 = 13
The pH of rainwater collected in a certain region of the
northeastern United States on a particular day was
4.82. What is the H+ ion concentration of the
rainwater?
pH = -log [H+]
[H+] = 10-pH = 10-4.82 = 1.5 x 10-5 M

The OH- ion concentration of a blood sample is 2.5 x 10-7 M.

What is the pH of the blood?
pH + pOH = 14.00
pOH = -log [OH-] = -log (2.5 x 10-7) = 6.60

pH = 14.00 – pOH = 14.00 – 6.60 = 7.40

15.3
 Equations and practice

•  You will need to memorize the following:

[H+] = 10–pH
[OH–] = 10–pOH
pH = – log [H+]
pOH = – log [OH–]
pH + pOH = 14
 The pH Scale
Measuring pH
•  Most accurate method to measure pH is to use a pH meter.
•  However, certain dyes change color as pH changes. These are
indicators.
•  Indicators are less precise than pH meters.
•  Many indicators do not have a sharp color change as a function of pH.
•  Most indicators tend to be red in more acidic solutions.

pH (indicator) paper pH meter

The pH Scale
 Equilibria  Involving    
Weak  Acids  and  Bases  
Consider acetic acid, HC2H3O2 (HOAc)
HC2H3O2 + H2O H3O+ + C2H3O2 -
Acid Conj. base

[H3 O+ ][OAc - ]
Ka = = 1.8 x 10 -5
[HOAc]

(K  is  designated  Ka  for  ACID)  

K  gives  the  raDo  of  ions  (products)  to  molecule  (reactants)  

Note : [H+] is a shorthand of [H3O+].

 Equilibria  Involving  A  Weak  Acid  
Consider 1.00 M acetic acid.
Calculate the equilibrium concentrations of
acetic acid (HOAc), H3O+, acetate (OAc-),
and the pH.

Step 1. Define equilibrium concs. in ICE table.

[HOAc] [H3O+] [OAc-]
Initial 1.00 0 0
Change -x +x +x
Equil 1.00-x x x
 Step 2. Write Ka expression
[H O + ][OAc - ] x 2
Ka = 1.8 x 10 -5 = 3 =
[HOAc] 1.00 - x

This  is  a  quadra@c.  Solve  using  quadra@c  

formula.  

or you can make an approximation if x is very small!

(Rule of thumb: 10-5 or smaller is ok)

We  can  ignore  the  (-­‐x)  in  the  denominator  if  the  acid  
dissociates  less  than  5%  
Step 3. Solve Ka expression
[H O + ][OAc - ] x 2
Ka = 1.8 x 10 -5 = 3 =
[HOAc] 1.00 - x

First  assume  x  is  very  small  because  Ka  is  

so  small.  
2
x
Ka = 1.8 x 10-5 =
1.00
Now  we  can  more  easily  solve  this  
approximate  expression.  
Step 3. Solve  Ka  approximate  expression    
2
x
Ka = 1.8 x 10-5 =
1.00

x    =    [H3O+]  =  [H+]  =[OAc-­‐]  =  4.2  x  10-­‐3  M  

pH  =  -­‐  log  [H+]    =    -­‐log  (4.2  x  10-­‐3)    =    2.37  

Note : [H+] is a shorthand of [H3O+].

 Equilibrium  Constants    
for  Weak  Bases  

Weak  base  has  Kb  <  1  .  

Leads  to  small  [OH-­‐]  and  a  pH  of  12  –  7.    
Rela@on  
of  Ka,  Kb,  
[H+]  and  
pH  
 Equilibria  Involving  A  Weak  Base  
Consider  0.010  M  NH3.    
Calculate  the  pH.  
   NH3    +    H2O                          NH4+      +        OH-­‐  
   Kb  =  1.8  x  10-­‐5  
Step 1. Define equilibrium concs. in ICE table
[NH3] [NH4+] [OH-]
IniDal     0.010 0 0
Change     -x    +x    +x  
Equilib 0.010  -­‐  x  x      x  
Step  2.  Solve  the  equilibrium  expression  

[NH + ][OH- ] x 2
Kb = 1.8 x 10-5 = 4 =
[NH3 ] 0.010 - x

Assume  x  is  small,  so  

       x  =  [OH-­‐]  =  [NH4+]  =  4.2  x  10-­‐4  M  
and  [NH3]  =  0.010  -­‐  4.2  x  10-­‐4  ≈    0.010  M  
The  approxima@on  is  valid!  
 
Step  3.  Calculate  pH  
[OH-­‐]  =    4.2  x  10-­‐4  M  
so  pOH  =  -­‐  log  [OH-­‐]    =    3.37  
Because  pH  +  pOH  =  14,  
pH  =  10.63  
 The pH Scale
Why  do  we  want  to  know  the  pH?  
•  In  biochemistry,  most  of  the  acids  encountered  are  
weak  acids  (Not  completely  dissociated).  
 
•  These  have  a    Ka  <<<  1.  

•  Important  biological  macromolecules  lose  acDvity  

at  extremes  of  pH.  

•  Some  drasDc  physiological  consequences  can  result  

from  pH  fluctuaDons  in  the  body.  
 Buffers  
Buffer
 
•  A  soluDon  that  resists  change  in  pH  
–  Typically  a  mixture  of  the  acid  and  base  form  of  a  
chemical  
–  Can  be  adjusted  to  a  parDcular  pH  value  
•  Why  use  them?  
–  Enzyme  reacDons  and  cell  funcDons  have  
opDmum  pH’s  for  performance  
–  Important  anyDme  the  structure  and/or  acDvity  of  
a  biological  material  must  be  maintained  
 Buffered  Solu@ons  
Composition and Action of Buffered Solutions

•  A  buffer  consists  of  a  mixture  of  a  weak  acid  (HX)  and  its  
conjugate  base  (X-­‐)  
 Buffered  Solu@ons  
A  buffer  soluDon  has  the  ability  to  resist  changes  in  pH  
upon  the  addiDon  of  small  amounts  of  either  acid  or  base.  

The effect of adding acid or base to an unbuffered solution.

The effect of adding acid or base to a buffered solution.

 How  buffers  work?  
•  Equilibrium  between  acid  and  base.  
 
Weak  acids  are  in  equilibrium  with  their  ionized  
species:                      
Governed  by  the  Law  of  Mass  AcDon,  and  
characterized  by  an  equilibrium  constant:  

⇌    
HA                    H+  +  A-­‐  
  -­‐
  [H+][A ]  
Keq  =      
[HA]  
 
 [H +][A-­‐]  
⇌    
HA                    H+  +  A-­‐                        Keq  =        
[HA]  
 
Ka  =  [A ]  [H ]/  [HA]    
-­‐ +

         =  [conjugate  base]  [H+]  /  [weak  acid]  

•  First  rearrange  the  first  equaDon  and  solve  for  [H+]  
   [H+]  =  Ka  x  [acid]/[conjugate  base]  
•  Then  take  the  log  of  both  sides  
   log10[H+]  =  log10Ka  +  log10    [HA]  /  [A-­‐]    

-pH -pKa
Henderson-­‐Hasselbalch  Equa@on  
 Henderson-­‐Hasselbalch  
•  Henderson-­‐Hasselbalch  equaDon  
  [Conjugate base]
pH = pK a + log
  [Weak acid]

•  From  this  equaDon,  we  see  that  

–  when  the  concentraDons  of  weak  acid  and  its  
conjugate  base  are  equal,  the  pH  of  the  soluDon  
equals  the  pKa  of  the  weak  acid  
–  when  pH  <  pKa,  the  weak  acid  predominates  
–  when  pH  >  pKa,  the  conjugate  base  predominates  
 How  buffers  work?  
•  Acetate  buffer  
⇌            CH3COO-­‐    +  H+  
CH3COOH    ↔
                                                         minimal  
 

CH3COONa    à        CH3COO-­‐    +  Na+  

•  If  more  H+  (HCl)  is  added  to  this  soluDon,  it  simply  
shins  the  equilibrium  to  the  len,  absorbing  H+  (reacts  
with  CH3COO-­‐  )  
•  [H+]  remains  unchanged.    
 
 
CH3COO-­‐            +            H+    à  CH3COOH  
                     Mainly  from  CH3COONa                                                  HCl  
 How  buffers  work?  
•  Acetate  buffer  
CH3COOH    ↔      
⇌     3 -­‐   C H COO -­‐    +  H+  

CH3COONa    à        CH3COO    +  Na+  

•  If  OH-­‐  (NaOH)  is  added  then  the  equilibrium  shins  

to  the  right  
•  OH-­‐  reacts  with  CH3COOH  
•  [H+]  remains  unchanged.    

CH3COOH      +  OH-­‐  à

 
      C H3COO -­‐    +  H O  
2

CH3COOH      +  NaOH  à

 
     NaCH3COO    +  H2O  
 
Buffer  Ac@on  
ApplicaDon  of  Buffer  
 Buffers  
§  Buffers  are  extremely  important  in  chemistry  and  biology.      
§  They  maintain  a  nearly  consistent  pH  in  various  soluDons.      
 Buffers  
Buffers  are  extremely  important  in  chemistry  and  biology.    They  
maintain  a  nearly  consistent  pH  in  various  soluDons.      

§  Our  blood  must  maintain  a  pH  around  7.35-­‐7.45.    

§  If  the  pH  is  above  7.45  you  would  have  a  
condiDon  called  alkalosis.    
§   If  the  pH  is  below  7.35,  then  one  would  suffer  
from  acidosis.  
 Buffers  

§  Acidosis  leads  to  depression  of  the  nervous  

system.      
§  Mild  acidosis  can  result  in  dizziness,  
disorientaDon,  or  fainDng  
§  More  severe  acidosis  can  cause  coma,  or  death.    
 Buffers  
•  What  would  happen  to  the  pH  of  our  blood  if  
we  were  to  eat  acidic  foods,  such  as  apples,  
oranges,  or  limes?      

•  What  might  happen  to  the  pH  of  our  blood  if  
some  of  the  hydrochloric  acid  from  our  
stomach  were  to  seep  into  our  blood?        

The pH would be lower in both

§  Despite  the  possibility  of  pH  increases  or  decreases,  
the  body  maintains  a  nearly  constant  pH  of  7.4.      
 
§  The  body  uses  buffers  to  maintain  this  remarkable  
feat.  

What  is  a  buffer  and  how  does  it  work?  

What  is  a  buffer  and  how  does  it  work?  

A  buffer  consists  of  a  weak  acid  and  the  salt  of  its  
conjugate  base,  or  a  weak  base  and  the  salt  of  its  
conjugate  acid.  

Examples:  

HF       +     NaOH                     N aF     +     H OH  
w.a.   c.b.  

NH3    +    HCl                                  NH4Cl    

w.b.   c.a.  
 Buffer Capacity
Buffer capacity is the ability to resist pH change.

§  The   more   concentrated   the   components   of   a  

buffer,  the  greater  the  buffer  capacity.    
 
§  A   buffer   has   the   highest   capacity   when   the  
component  concentraDons  are  equal.  

pH  =  pKa  
 Buffer Range
Buffer range is the pH range over which the buffer acts effectively.

•  Buffers have a usable range within ± 1 pH unit of the

pKa of its acid component.
Table 2.7 pH values and base/acid ratios for buffers

pH [Base]/[Conjugate Acid]
pK a -3 1/1000
pK a -2 1/100
pK a -1 1/10
effective
pK a 1/1 buffer
pK a +1 10/1 range
pK a +2 100/1
pK a +3 1000/1
 Limits  to  the  working  range  of  a  buffer  
↔      CH3COO-­‐    +  H+  
CH3COOH        ⇌  
  CH3COO-­‐    +  H+    à  CH3COOH    
•  If  too  much  H+  is  added,  the  
equilibrium  is  shined  all  the  
way  to  the  len,  and  there  is  
no  longer  any  more  CH3COO-­‐  
to  “absorb”  H+.  
•  At  that  point  the  soluDon  no  
longer  resists  change  in  pH;  it  
is  useless  as  a  buffer.  
•  A  similar  argument  applies  to  
the  upper  end  of  the  working  
range.  
 Factors  in  choosing  a  buffer  
•  Be  sure  it  covers  the  pH  range  you  need  
–  Generally:  pKa  of  acid  ±  1  pH  unit  
–  Consult  tables  for  ranges  or  pKa  values  
•  Be  sure  it  is  not  toxic  to  the  cells  or  organisms  
you  are  working  with.  
•  Be  sure  it  would  not  confound  the  experiment  
(e.g.  avoid  phosphate  buffers  in  experiments  
on  plant  mineral  nutriDon).  
What  to  report  when  wri@ng  about  a  buffer?  

•  The  idenDty  of  the  buffer  (name  or  chemicals)  

•  The  molarity  of  the  buffer  
•  The  pH  of  the  buffer  
•  Examples:  
–  “We  used  a  0.5M  Tris  buffer,  pH  8.0.”  
–  “The  reacDon  was  carried  out  in  a  0.1M  boric  acid  
–  sodium  hydroxide  buffer  adjusted  to  pH  9.2.”    
Calcula@ng  buffer  recipes  
 Henderson-­‐Hasselbach  Equa@on  

•  Derived  from  the  equilibrium  expression  of  a  

weak  acid  and  the  pH  equaDon.  

 
•  This  equaDon  allows  you  to  determine  the  pH  
of  a  buffer  soluDon  
•  pKa    =  -­‐log  Ka  
 The  Common  Buffer  Problems  

1.  Compute  pH  of  a  buffer  given  the  actual  

concentra@ons  of  the  weak  acid  and  
conjugate  base.    
•  The  pH  is  easily  calculated  with:    
•  Example:    Determine  the  pH  in  which  1.00  
mole  of  H2CO3  (Ka  =  4.2  x  10-­‐7)  and  1.00  mole  
NaHCO3  dissolved  in  enough  water  to  form  
1.00  Liters  of  soluDon.  

pH    =    -­‐log  (4.2  x  10-­‐7)    +    log  (1.00M)/(1.00M)  

pH    =    pKa    =    6.4  
**    pKa  of  a  weak  acid  can  help  determine  pH  of  buffer  you  
will  make  if  it  is  mixed  in  a  1:1  mole  raDo!  
 Buffer  Exercise  
         How  many  moles  of  NaHCO3  should  be  added    
to  1  liter  of  0.100M  H2CO3  (Ka  =  4.2  x  10-­‐7  )  to  prepare  
a  buffer  with  a  pH  of  7.00?  
[HCO3-­‐]  
pH    =    pKa    +    log    
[H2CO3]  
7.00    =      -­‐log(4.2  x  10-­‐7)    +    log  [HCO3-­‐]  
                                                                                                         (0.100)  
0.60  =    log  [HCO3-­‐]  
                                         0.001      
[HCO3-­‐]    =    0.40  moles  should  
100.6    =    [HCO3-­‐]   be  added!  
                               0.100  
 pH  Shid  Problem  
 
If  you  add  2.00  mL  of  0.100  M  HCl  to  100  mL  of  a  
buffer  consisDng  of  0.100  M  HA  and  0.200  M  
NaA,  what  will  be  the  change  in  pH?    
 
•  Ka  of  HA  is  1.5x10-­‐5.            pKa  =  4.82.    
•  The  ini@al  pH  is:    
•  If  we  add  H+  to  the  equilibrium  system  it  will  react  with  the  
strong  conjugate  base  ‘A-­‐,  to  form  more  HA.  
H+  +    A-­‐  à  HA    
•  Set  up  an  ICE  chart  to  determine  how  the  mole  values  will  
change  using  stoichiometry!  
    2.00  m  L     of  0.100  M  HCl    
100  mL  of  a  buffer  consis@ng  of  0.100  M  HA  and  0.200  M  NaA  

mmoles H+ mmoles A- mmoles HA Volume, mL

Initial 0.200 20.0 10.0 100+2 mL

(2.00 mL of 0.100 M HCl) (100 mL of 0.200 M NaA) (100 mL of 0.100 M HA)

Final 0 19.8 10.2 102 mL

(20.0-0.2) (10.0+0.2)

Molarities 19.8/102 10.2/102

 Buffer Range
Buffer range is the pH range over which the buffer acts effectively.

•  Buffers have a usable range within ± 1 pH unit of the

pKa of its acid component.
Table 2.7 pH values and base/acid ratios for buffers

pH [Base]/[Conjugate Acid]
pK a -3 1/1000
pK a -2 1/100
pK a -1 1/10
effective
pK a 1/1 buffer
pK a +1 10/1 range
pK a +2 100/1
pK a +3 1000/1
  Titra@on  curve  of  ace@c  acid: