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Questions

From HW.
1.
 The Zn in a 0.7556-g sample of foot powder
was titrated with 21.27 mL of 0.01645 M
EDTA (Y4-). Calculate the percent Zn in this
sample. Moles of EDTA = Moles of Zn
(0.01645 M)(0.02127L) = Moles of Zn
0.0003498915= Moles of Zn
Convert to grams of Zn and compare to original value
0.0003498915 moles x 65.39 gram/mole = 0.022879 gram of Zn
0.022879 g
%Zn  x100%  3.0279%
0.7556 g
2.
 A 50.00-mL aliquot of a solution containing Iron (II)
required 13.73 mL of 0.01200 M EDTA (Y4-) when
titrated at pH 2.0. Express the concentration of
iron in parts per million.
Moles of EDTA = Moles of Fe2+
(0.01200 M)(0.01373L) = Moles of Fe2+
0.00016476 = Moles of Fe2+

2 0.00016476mole 0.0032952mole
Fe , M  
0.0500 L 1L
2.
 A 50.00-mL aliquot of a solution containing Iron (II)
required 13.73 mL of 0.01200 M EDTA (Y4-) when
titrated at pH 2.0. Express the concentration of
iron in parts per million.

0.0032952mole 55.847 g 1000mg  184.0mg


x x
1L mole 1g L
13-5.
 Calculate the conditional constants for the
formation of EDTA complex of Fe2+ at a pH of
(a) 6.0, (b) 8.0, (c) 10.0.
K’f = a Kf

KKK’f’f’f=
==5.6
0.36
2.3xx(1.995
10
10-3-5(1.995
(1.995
x 1014)
xx101014)
14)

= 7.182
KK’f’f = 4.589
1.117 xx 10
1013
912
4.
 Derive a titration curve for 50.00 mL of 0.01000 M Sr2+ with 0.02000 M
EDTA in a solution buffered to pH 11.0. Calculate pSr values after the
addition of 0.00, 10.00, 24.00, 24.90, 25.00, 25.10, 26.00, 30.00 mL of
titrant.

At initial Point Find equivalence Volume


pSr = -log (0.0100)
Moles Sr2+ = Moles EDTA
At initial Point (0.05000 L)x(0.01000M Sr2+) = 0.02000 M x Ve
pSr = 2.000
25.0 mL = Ve
4.
 Derive a titration curve for 50.00 mL of 0.01000 M Sr2+ with 0.02000 M
EDTA in a solution buffered to pH 11.0. Calculate pSr values after the
addition of 0.00, 10.00, 24.00, 24.90, 25.00, 25.10, 26.00, 30.00 mL of
titrant. Excess will determine pSr

Sr2+ + Y4- -> SrY2-


Before ?
0.0005000 moles 0.0002000 moles None

After 0.0003000 moles None 0.0002000 moles

 0.0003000moles 
pSr   log    2.3010
 0.05000 L  0.01000 L 
4.
 Derive a titration curve for 50.00 mL of 0.01000 M Sr2+ with 0.02000 M
EDTA in a solution buffered to pH 11.0. Calculate pSr values after the
addition of 0.00, 10.00, 24.00, 24.90, 25.00, 25.10, 26.00, 30.00 mL of
titrant. Excess will determine pSr

Sr2+ + Y4- -> SrY2-


Before ?
0.0005000 moles 0.0004800 moles None

After 0.0000200 moles None 0.0004800 moles

 0.00002000moles 
pSr   log    3.568
 0.05000 L  0.02400 L 
4.
 Derive a titration curve for 50.00 mL of 0.01000 M Sr2+ with 0.02000 M
EDTA in a solution buffered to pH 11.0. Calculate pSr values after the
addition of 0.00, 10.00, 24.00, 24.90, 25.00, 25.10, 26.00, 30.00 mL of
titrant. Excess will determine pSr

Sr2+ + Y4- -> SrY2-


Before ?
0.0005000 moles 0.0004980 moles None

After 0.00000200 moles None 0.0004980 moles

 0.000002000moles 
pSr   log    4.5735
 0.05000 L  0.02490 L 
4.
 Derive a titration curve for 50.00 mL of 0.01000 M Sr2+ with 0.02000 M
EDTA in a solution buffered to pH 11.0. Calculate pSr values after the
addition of 0.00, 10.00, 24.00, 24.90, 25.00, 25.10, 26.00, 30.00 mL of
titrant. Equivalence
- EQUILIBRIUM OF SrY2- is source of Sr2+

Sr2+ + Y4- -> SrY2-


Before 0.0005000 moles 0.0005000 moles None

After None None 0.0005000 moles


4.
 Derive a titration curve for 50.00 mL of 0.01000 M Sr2+ with 0.02000 M
EDTA in a solution buffered to pH 11.0. Calculate pSr values after the
addition of 0.00, 10.00, 24.00, 24.90, 25.00, 25.10, 26.00, 30.00 mL of
titrant. Equivalence
- EQUILIBRIUM OF SrY2- is source of Sr2+

Sr2+ + Y4-  SrY2-


I None None 0.0005000 moles/ 0.075 L

C +x +x -x

E +x +x 0.00666 –x
2
[ SrY ] [0.0066  x] x  3.94 106
K = 4.25 x 10  4
’ 8
3 
[Y ][ Sr ] [ x][ x] pSr = 5.40
4.
 Derive a titration curve for 50.00 mL of 0.01000 M Sr2+ with 0.02000 M
EDTA in a solution buffered to pH 11.0. Calculate pSr values after the
addition of 0.00, 10.00, 24.00, 24.90, 25.00, 25.10, 26.00, 30.00 mL of
titrant. Post equivalence
- EQUILIBRIUM OF SrY2- is source of Sr2+

Sr2+ + Y4-  SrY2-


I None 0.000002/0.0751 L 0.0005000 moles/ 0.0751 L

C +x +x -x

E +x 2.666x10-5 +x 0.006657 –x
2
[ SrY ] [0.006657  x]   7
K = 4.25 x 10  4
’ 8
3 
x 5.205 10
[Y ][ Sr ] [ x][ 2.666 105  x] pSr = 6.2835
4.
 Derive a titration curve for 50.00 mL of 0.01000 M Sr2+ with 0.02000 M
EDTA in a solution buffered to pH 11.0. Calculate pSr values after the
addition of 0.00, 10.00, 24.00, 24.90, 25.00, 25.10, 26.00, 30.00 mL of
titrant. Post equivalence
- EQUILIBRIUM OF SrY2- is source of Sr2+

Sr2+ + Y4-  SrY2-


I None 0.00002/0.076 L 0.0005000 moles/ 0.076 L

C +x +x -x

E +x 2.63x10-4 +x 0.006578 –x
2
[ SrY ] [0.006578  x] x  5.885 10 8
K = 4.25 x 10  4
’ 8

[Y ][ Sr 3 ] [ x][ 2.63 104  x] pSr = 7.230
4.
 Derive a titration curve for 50.00 mL of 0.01000 M Sr2+ with 0.02000 M
EDTA in a solution buffered to pH 11.0. Calculate pSr values after the
addition of 0.00, 10.00, 24.00, 24.90, 25.00, 25.10, 26.00, 30.00 mL of
titrant. Post equivalence
- EQUILIBRIUM OF SrY2- is source of Sr2+

Sr2+ + Y4-  SrY2-


I None 0.0001000/0.080 L 0.0005000 moles/ 0.080 L

C +x +x -x

E +x 0.00125 +x 0.00625 –x
2
[ SrY ] [0.00625  x] x  1.176 x10 8
K = 4.25 x 10  4
’ 8

[Y ][ Sr 3 ] [ x][0.00125  x] pSr = 7.929
9
8
7
6
5
pSr

4
3
2
1
0
0 10 20 30 40
Volume Titrant
Section 23-3
A Plumber’s View of
Chromatography

The chromatogram
“Retention time”
“Relative retention time”
“Relative Retention”
“Capacity Factor”
A chromatogram
Retention time (tr) – the time required for a substance to pass from one
end of the column to the other.
Adjusted Retention time – is the retention time corrected for dead volume
“the difference between tr and a non-retained solute”
A chromatogram
Adjusted Retention time (t’r) - is the retention time corrected for dead
volume “the difference between tr and a non-retained solute”
A chromatogram
Relative Retention (a) -the ratio of adjusted retention times for any two
components. The greater the relative retention the greater the separation.
Used to help identify peaks when flow rate changes.
t 'r 2
a where t 'r1  t 'r 2  so a  1
t 'r1
A chromatogram
Capacity Factor (k’) -”The longer a component is retained by the column,
the greater its capacity factor. To monitor performance of a column – one
should monitor the capacity factor, the number of plates, and peak
asymmetry”.
tr  tm
k'
tm
An Example
A mixture of benzene, toulene, and methane was injected into
a gas chromatograph. Methane gave a sharp peak in 42
sec, benzene was @ 251 sec and toulene eluted at 333
sec. Find the adjusted retention time (for each solute), the
capacity factor (for each solute) and the relative retention.
Adjusted retention time (t’r) = total time – tr (non retained component)
t’r(benzene) = 251 sec – 42 sec = 209 s
t’r (toulene) = 333-42 sec = 291 s
An Example
A mixture of benzene, toulene, and methane was injected into
a gas chromatograph. Methane gave a sharp peak in 42
sec, benzene was @ 251 sec and toulene eluted at 333
sec. Find the adjusted retention time (for each solute), the
capacity factor (for each solute) and the relative retention.
Capacity Factor (k’) -”The longer a component is retained by the column, the greater
its capacity factor. To monitor performance of a column – one should monitor the
capacity factor, the number of plates, and peak asymmetry”.

tr  tm t r  t m 251  42
k' k 'benzene   = 5.0
tm tm 42
An Example
A mixture of benzene, toulene, and methane was injected into
a gas chromatograph. Methane gave a sharp peak in 42
sec, benzene was @ 251 sec and toulene eluted at 333
sec. Find the adjusted retention time (for each solute), the
capacity factor (for each solute) and the relative retention.
Capacity Factor (k’) -”The longer a component is retained by the column, the greater
its capacity factor. To monitor performance of a column – one should monitor the
capacity factor, the number of plates, and peak asymmetry”.

tr  tm t r  t m 333  42
k' k 'toulene   = 6.9
tm tm 42
An Example
A mixture of benzene, toulene, and methane was injected into
a gas chromatograph. Methane gave a sharp peak in 42
sec, benzene was @ 251 sec and toulene eluted at 333
sec. Find the adjusted retention time (for each solute), the
capacity factor (for each solute) and the relative retention.
Relative Retention (a) -the ratio of adjusted retention times for any two components.
The greater the relative retention the greater the separation. Used to help identify
peaks when flow rate changes.

t 'r 2 t 'toulene 291sec


a a   1.39 sec
t 'r1 t 'benzene 209 sec
Efficiency of Separation

“Two factors”
1) How far apart they are (a)
2) Width of peaks
Resolution
Resolution

t r 0.589t r
Resolution  
w av w1/ 2 av
Example – measuring
resolution
 A peak with a retention time of 407 s has a width at the
base of 13 s. A neighboring peak is eluted at 424 sec with
a width of 16 sec. Are these two peaks well resolved?

t r 424  407
Resolution  Resolution   1.17
w av (13  16) 2
1
Data Analysis
The Inlet
Why are bands broad?

Diffusion and flow related effects


Of particular concern in Gas Chromatography.
Why?
Diffusion is faster
Gases from the headspace of a beer can!!
Packed column ... Compare
peak widths with your
sample

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