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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
  
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 |  r  g

## nd, since Kw =[H+ [OHg

pH + pOH = 14


¬  
|   
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.

acidic proton.


## 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
 

       `  `

 ! 
! !   
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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)

## 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

r
3   

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

## jater acting as a base:

Ô @  @  Ô @ gÔ @


j  
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gÔ @  @  "@  Ô @


Salts of polyprotic acids can also be amphoteric:

## 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

(acid)

j 
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## 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.

## 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.
ñ
ñ
ñ


Oa÷÷
\$    
Electron withdrawing effects through sigma bonds

 
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! ! ! !! 
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
Similarly,

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
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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.

?     ! 

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 
 

 
!

## 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

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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
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
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##   g  

j   
  
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j
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  m mm 
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? ! #   \$
 %

! ! &
  '( |  '

Consider an acetate buffer equilibrium:
Hc + H2O  cg + H3O+

## H3O+ + cg | H2O + Hc ! ! ! ÚÚ Ã 

Ô  Ã   Ú
The reaction goes effectively to completion due to the large K!

## Virtually all the added acid is absorbed.

Hc + H2O  cg + H3O+

## Similarly for added OHg to an acetate buffer

Ô  Ã  Ú 
OHg + Hc | H2O + cg ! ! ! !   Ã 
  `  

## Strong acid added to weak base goes to completion

Strong base added to weak acid goes to completion

## '  ! ( !) 

! *

!  
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
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
 |    
  | 


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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 
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

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

## 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:

