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The proton concentration (and hydroxide concentration) are so


important we will follow them with a new concept pH. In general
these concentrations are small but if the hydrogen ion concentration
in your blood increases from 3x10-7 M to 3x10-6M, you are probably
dead. < 
  
 

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nd, since Kw =[H+ [OHg

pH + pOH = 14


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|   
jhat is the pH, pOH and concentration of all species present in a solution
0.25ï HCN?

HCN is a weak acid and therefore we need to use the weak acid box:

HCN ļ H+ + CNí
Init 0.25 0 0 `
    î 
change -x x x Ú î `
Eq 0.25-x x x `   îÚ

jhat are concentrations of all species:


[HCN = 0.25M; [H+ =1.1x10-5; [CN- =1.1x10-5M; pH = 4.96; pOH = 9.04

Now compute pH = -log(1.1x10-5) = 4.95


pOH = 9.05


3   ÷

Ú
3olyprotic cids contain more than one
acidic proton.

So far we have considered acids with only


one acidic proton (HF, HNO3, HOCl)

Some have had more than one proton


(CH3COOH), but only one was acidic.

Now consider those with more than one


acidic proton.

Have already considered H2SO4:

H2SO4 + H2O ĺ H3O+ + HSO4g Ka very large


HSO4g + H2O  H3O+ + SO4= Ka = 1.2x10-2

Second dissociation is weaker than first


(generally true for polyprotic acids)

°
Consider 0.10M H2SO4:

H2SO4 + H2O ĺ H3O+ + HSO4g Ka very large


HSO4g + H2O  H3O+ + SO4= Ka = 1.2x10-2
I 0.10 0.10 0
C -x +x +x
E 0.10-x 0.10+x x
 

       `  `

 ! 
! !   
      ` 
Making the usual approximations, x = [SO4-2 = 0.012M


Is the approximation valid?
`
!
  
!  
No!
   

So use quadratic and x = 1.97x10-2


[H+ = 0.120 (instead of 0.1)

jhat is the pH of 0.10M sulfuric acid?

pH = -log[H3O+ = -log(.12) = 0.92

©
jhat about a polyprotic acid with two weak acid
protons, like H2CO3?

H2CO3 + H2O  H3O+ + HCO3g Ka=4.3x10-7


HCO3g + H2O  H3O+ + CO3-2 Ka=5.6x10-11

jhat is the pH of 0.20M H2CO3?

r
jhat is the pH of 0.20M H2CO3? Look at 1st step 1st

H2CO3 + H2O  H3O+ + HCO3g Ka=4.3x10-7


 
` `
    
`  î° X = 2.93x10-4
  î `  
Do we need to worry about 2nd step? 
HCO3g + H2O  H3O+ + CO3-2 Ka=5.6x10-11
I 2.93x10-4 2.93x10-4 0
C -x x x
E 2.93x10-4-x 2.93x10-4+x x

 
î  `  ` 
  î
 Ú î X = 5.6x10-11M
 
`  î ` 
rr
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a a   ÷ a
 
Try a problem: jhat is the pH of a 0.15 M
solution of ascorbic acid (vitamin C, H2C6H6O6)?

Ka1 = 7.9x10-5
Ka2 = 1.6x10-12

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jater can be both a base or an acid ± it is an
amphoteric substance.

jater acting as a base:


Ô @  @  Ô @ gÔ @


j  
 
gÔ @  @  "@  Ô @



Salts of polyprotic acids can also be amphoteric:

H2CO3  HCO3g  CO3-2 Ka1 = 4.3x10-7, Ka2 = 5.6x10-11

H2CO3  HCO3g + H+ Ka1 = 4.3x10-7 (acid)


CO3-2 + H2O  HCO3g + OH g Kb = Kw/Ka2
Kb=1.8x10-4 (base)

But what about the middle one? HCO3g

r
H2CO3  HCO3g  CO3-2 Ka1 = 4.3x10-7, Ka2 = 5.6x10-11

HCO3g can accept a proton(base) or donate a proton


(acid)

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HCO3g  H+ + CO3-2 Ka Ka2 = 5.6x10-11

HCO3g +H2O H2CO3 + OH g Kb = Kw/Ka1 =


10-14/4.3x10-7 = 2.3x10-8
Kb >> Ka, so it acts as a base

3roblem to work:

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To eliminate the exponents, it is common to


report pK values rather than K values. Note
that the ³p´ means ±log.

So if Ka = 10-11, then pKa = 11

nd note that the larger the pKa, the smaller


the Ka and the weaker the acid.

r
¬
 
jhy is ethanol, CH3CH2OH (pKa 17) so much weaker
an acid than acetic acid, CH3COOH (pKa 4.72)?
The answer lies in the stability of the product of the
Ka reaction:

CH3CH2OH + H2O  CH3CH2Og + H3O+ ¬ 



CH3COOH + H2O  CH3COOg + H3O+  

Resonance stabilization of acetate draws equilibrium

to right.
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Electron withdrawing effects through sigma bonds

 
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In the previous cases the acid hydrogen was always bonded


to oxygen, and electron density was being drawn away from
the O-H bond.

Here the bond itself is different in each acid. The




acid strength is due to 
bond strength.

6


6

H+ + OHg  H2O
eg eg
acceptor donor

H+ + NH3  NH4+
eg acceptor eg donor

cid/base reactions can be defined in terms of electron


pair acceptor (acid) and electron pair donor (base). This
is the formalism used in the Lewis cid/Base framework.


?     ! 

!    
 
 

 
!

F3B + NH3  F3BNH3


eg acceptor eg donor
Lewis acid Lewis base

cid is electron acceptor


Base is electron donor

Because boron can form electron deficient compounds, it


often acts as a Lewis acid


?! "  6

Fe3+ + 6 NCg  Fe(CN)63g


eg acceptor eg donor


? ?   
  



Model cid Base


rrhenius proton hydroxide strong acids

Bronsted proton donor proton acceptor strong acids+weak


acids

Lewis electron pair electron pair strong acids; weak


acceptor donor acids; other non-proton
compounds


  

r
The Ka for NaH23O4 is

1. 7.5x10-3
2. 6.2 x10-8
3. 4.8 x10-13


The Kb for NaH23O4 is

1. 1.3x10-12
2. 1.6x10-7
3. 0.021


CH3CH2CO2Na is

1.n acid
2. base
3.Neither
4.I¶m lost


(CH3)2NH is

1.n acid
2. base
3.Neither
4.I¶m lost


CH3NH3Cl is

1.n acid
2. base
3.Neither
4.I¶m lost


jhich of the following could act
as a Lewis cid?

1.NH3
2.H2O
3.NH4+
4.l3+


jhich of the following could act
as a Lewis Base?

1.NH3
2.BF3
3.NH4+
4.l3+


Gou mix a solution of a strong acid with a
pH of 4 and an equal volume of a strong
acid solution with a pH of 6. Is the final pH

1.less than 4
2.between 4 and 5
3.5
4.between 5 and 6
5.greater than 6
6.I am lost


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Consider an acetate buffer equilibrium:
Hc + H2O  cg + H3O+

jhen a strong acid is added to a Hc/cg buffer solution,

H3O+ + cg | H2O + Hc ! ! ! ÚÚ Ã 


Ô  Ã   Ú
The reaction goes effectively to completion due to the large K!

Virtually all the added acid is absorbed.


Hc + H2O  cg + H3O+

Similarly for added OHg to an acetate buffer


Ô  Ã  Ú 
OHg + Hc | H2O + cg ! ! ! !   Ã 
  `  

It is a general result to say:

Strong acid added to weak base goes to completion


Strong base added to weak acid goes to completion

So if you have a buffer equilibrium: H + H2O  g + H3O+

'  ! ( !) 


! *

!  
jhich of the following could be used to make a buffer?

1.HF and KF
2.CH3NH2 and CH3NH3Cl
3.NaOH and HCl
4.NaOH and HNO2
5.HCl and NH3
6.K2H3O4 and NaOH
7.K2H3O4 and HNO3


!   |

Ú
jhat is the pH of a buffer made by mixing 0.10mol HF and
0.2mol NaF to 1000ml of water?

HF + H2O  Fg + H3O+
I 0.1 0.2 0 (ignoring auto-ionization of water)
C -x +x +x
E 0.1-x 0.2-x x
Ka = 7.2x10-4
Make the usual approximations to get:

 `
  °  î  Solving, x = [H3O+ = 3.6x10-4
 pH = -log(3.6x10-4) = 3.4

Note that the pH depended on the ratio of base to acid and


on the value of the Ka.

Úr
Consider a hypochlorous buffer made by adding HOCl and
NaOCl to the same solution.

The governing equilibrium is


HOCl + H2O  OClg + H3O+

 î  Y


 
Y  
s before, the hydrogen ion concentration depends on the
ratio of base and acid:

  

  ! Ô
  
Ú
  

  ! Ô
  
This can be rearranged by taking the negative log of both
sides:

  
  
  !   Ô   
 
  
 !  Ô  
 
ºeneralizing,


Y     
 
Ú


 !  Ô  
Ô 
aka the Henderson-Hasselbalch equation

Two important observations to be made here:


1.jhen the concentrations of weak acid and conjugate base
are equal, pH = pKa
2.This equation is based on assumed approximations.


 `  
   Ô
 
  
Ô! }
Ô  `  Ô 

jhen the approximations are not valid, the Henderson-


Hasselbalch equation is not valid.
Ú
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Y     
 
There must be some weak base present to absorb added H+
and
There must be some weak acid present to absorb added OHg

In practical terms, this means



 should be kept
between 0.1 and 10.  
+, 

'

!-


!! ÚÚ
jhat acid/base pair would you choose to buffer at pH 6.5?

Ú
?./* 0
jhat acid/base pair would you choose to buffer at pH 5.0?

1. mmonia/conj acid jhen given a Kb or pKb, you


2. Methylamine/conj acid must convert it to the pKa to
3. Ethylamine/conj acid determine the pH range for the
4. niline/conj acid buffer.
5. 3yridine/conj acid
6. I¶m lost
Ú°
jhat acid/base pair would you choose to buffer at pH 7.4?

Ú
 

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Y     
 
jhat is the pH of a buffer containing 0.15M NH3 and 0.40M
NH4ClO3? Ka (NH4+) = 5.55x10-10

 & This suggests way


pKa = -log(5.55x10-10) = 9.26
too much precision ± you
 Ú will be lucky to be at
 !    ! 
pH = 8.8±0.5

Ú©
jhat is the approximate pH of a buffer that contains
0.2M KHCO3 and 0.3M K2CO3?

K+ is a spectator ion: active species are


HCO3g and CO3-2
Ka of the weak acid HCO3g is 5.6x10-11, pKa =10.3




 !  Ô   ! 
  ! Ú
Ô   
jhat is the approximate pH of a buffer that contains
0.1M KH23O4 and 0.3M KH3O4?

1. 2.6
2. 7.7
3. 12.8
4. 1.7
5. 6.7
6. 11.8 r
 small note about nomenclature.

jhen we say we have a 0.20M fluoride buffer,


we mean that [HF +[Fg = 0.20

So a buffer that contains 0.20M H2CO3 and 0.10M


KHCO3 is called a 0.30M carbonate buffer.


ust to review where we are:

 buffer consists of a weak acid/weak base conjugate pair

 buffer works through Le Chatelier¶s 3rinciple

The pH range of a given buffer pair is pKa 1

The pH of a buffer can be calculated using pH = pKa + log(b/a)