EXPERIMENT 2

TITLE : Determination of Composition of Complexes using Job Meto!

"#JECTI$E :
1. To learn the UV-Vis spectroscopy method
2. To determine the composition of complexes using Job Method
3. To obtained UV-Vis spectrum for ic!el "ulphate solution and #thylene ligand
solution
T%E"R& :
Job Method is often used to determine the soluble i
2$
- en complexes. This
method can be used to calculate the %n& 'alue of the complexes inside the solution.
( $ n) ()
n
*1+
,n this experiment - ( represent i
2$
and ) is ethylene diamine *en+. ,n a system
.ith a mixture of metal i
2$
and ligand en. /ifferent types of complexes may formed- for
example i*en+
2$
- i*en+
2
2$
- i*en+
3
2$
and many more.
The e0uilibrium e0uation is as belo.1
i
2$
$ en i*en+
2$
2
1
*1a+
i*en+
2$
$ en i*en+
2
2$
2
2
*1b+
i*en+
2
2$
$ en i*en+
3
2$
2
3
*1c+
"pecies that formed the most in the solution depends on the relati'e 'alue of the
e0uilibrium constant. ,f the 'alue of 2
2
is bigger than 2
1-
that means the concentration of
i*en+
2
2$
is higher that i*en+
2$
. ,n this case- to trace the concentration of i*en+
2$
may
be difficult. Job method is only applicable to systems .ith e0uilibrium constants that 'ary
a lot such as this system i
2$
-en.
The absorption at certain .a'elength depends on the concentration of the species.
,n this experiment- e'ery solution prepared contains the same concentration of ( and ).
This is to ensure that the 'alue of e0uilibrium constant of the formation of (*)+
n
is large
and the absorption for the species is maximum .hen the concentration of ligands en is
exactly %n& times the concentration of ion (. The 'alue of %n& *.hich is the composition
of the complexes (*)+
n
can be calculated if the concentration rate of )3( is !no.n for the
solution that gi'e the maximum absorption.
The solutions that contain metal ion ( are mixed to the solution of ligand )- both
at the same concentration *M mol dm
-3
+. 4 series of solutions .ere prepared by adding 5
dm
3
solution of ligand to *1-5+ dm
3
of metal ion. The total concentration of metal ion and
ligand in each solution must be the same as M concentration. 4t e0uilibrium- (- ) and
()
n
are labeled 6
1
- 6
2
- and 6
3
respecti'ely. The e0uation for each solution is gi'en as
belo.1
6
1
7

M*1-5+-6
3
*2+
6
2
7

M5+-n6
3
*3+
6
3
7

26
1
6
2
n *8+
9hereby 2 is the e0uilibrium constant at 5 is the mole fraction of ligand.
4t the maximum point for graph 6
3
's 5
d6
3
7 : *;+
dx
/ifferentiate e0uations *8+- *3+ and *2+ and by using e0uations *2+- *3+ and *;+- .e can get
n 7 5
1-5 *<+
This pro'ed that by using the 'alue of 5 .here 6
3
is maximum- the 'alue of n can be
calculated.
#eer's La(
4 7 =bc *>+
= for (- ) and ()
n
at certain .a'elength are present as =
1-
=
2
and =
3
. The absorption for the
solution is a mixture of the absorption for each species .hich absorb at different
.a'elength.
4 7 ?=
1
6
1
$ =
2
6
2
$ =
3
6
3
@b
3
*A+
,f there is no reaction bet.een ( and )- 6
3
.ill be Bero and the e0uation for absorption
becomes
4
($)
7 ?=
1
M*1-5+ $ =
2
M5@b *C+
The difference bet.een 4 and 4
B$)
is represent as *symbol D+
D 7 4 E 4
B$)
D 7 ?=
1
6
1
$ =
2
6
2
$ =
3
6
3
- =
1
M
1
*1-5+ - =
2
M5@b *1:+
From e0uation *1:+- .e can see that .hen the 'alue of D is maximum .hen 6
3
is
maximum if =
3
G =
1.
D .ill ta!e the minimum 'alue .hen 6
3
is maximum if =
3
H =
1
.
MET%"D"L")& :
1::cm
3
of nic!el sulfate *i"I
8
.<J
2
I+ *:.8M+and 1::cm
3
of
ligand-en *:.8M+ .as prepared.

The spectrum of i"I

8
and ligand-en in the range of
*2::-A::nm+ .ere obtained.

1:cm
3
of ligand .ith mole fraction of :.3-:.8- :.;- :.<-
:.>- :.A and :.C .ere prepared.

The spectrum in the range of ;:: E <;:nm .ere recorded.

The 'alue of D .ith at least fi'e different .a'elengths *;3:- ;8;- ;>A- <22 and <8:nm+
.ere calculated and 5 's D for each results .as plotted.

The 'alue of 5 .hen D at the maximum for each graph .as determine.

The n 'alues for i*en+

n
2$
complexes .as calculated by using the
'alue of 5 in e0uation *<+.









Result:
The 'alue of absorption at certain K for mixture i
2$
and ligand-en

at different mole
fraction.
Table of ligand mole fraction .ith using 'olume of nic!el and ligand-en
o )igand mole fraction-5 Volume of ligand-en 3ml Volume of nic!el 3ml
1 :.3 3.: >.:
2 :.8 8.: <.:
3 :.; ;.: ;.:
8 :.< <.: 8.:
; :.> >.: 3.:
< :.A A.: 2.:
> :.C C.: 1.:

K 3 nm 4
B
4bsorption of nic!el
;3:.: :.13A
;8;.: :.1;1
;>A.: :.22C
<22.: :.;8A
<8:.: :.>2>
Cal*ulation
6alculation of 'alues D .ith different K and mole fraction.
D 7 ?4 E *1-5+4
B
@b
4 1 absorption at certain K and certain ligand mole fraction.
4
B
1 absorption of nic!el at certain K
5 1 ligand-en mole fraction
L 1 siBe3long cell .as used is 1cm.
1. 4t K 7 ;3:.:nm
2. 4t K 7 ;8;.:nm
X A2 Az b Y/cm
0.3 0.141 :.1;1 1 [0.141 - ( 1-0.30 ) :.1;1 (1) = 0.0353
0.4 0.150 :.1;1 1 [0.150 - ( 1-0.40 ) :.1;1](1) = 0.0594
0.5 0.156 :.1;1 1 [0.156 - ( 1-0.50 ) :.1;1](1) = 0.0805
0.6 0.163 :.1;1 1 [0.163 - ( 1-0.60 ) :.1;1](1) = 0.1026
0.7 0.187 :.1;1 1 [0.187 - ( 1-0.70 ) :.1;1](1) = 0.1417
0.8 0.231 :.1;1 1 [0.231- ( 1-0.80 ) :.1;1](1) = 0.2008
0.9 0.316 :.1;1 1 [0.316- ( 1-0.90 ) :.1;1](1) = 0.3009
3. 4t K 7 ;>A.:nm
X A3 Az b Y/cm
0.3 0.245 :.22C 1 [0.245 - ( 1-0.30 ) :.22C](1) = 0.0847
0.4 0.260 :.22C 1 [0.260- ( 1-0.40 ) :.22C](1) = 0.1226
0.5 0.281 :.22C 1 [0.281 - ( 1-0.50 ) :.22C](1) = 0.1665
0.6 0.293 :.22C 1 [0.293 - ( 1-0.60 ) :.22C](1) = 0.2014
0.7 0.313 :.22C 1 [0.313 - ( 1-0.70 ) :.22C](1) = 0.2443
0.8 0.328 :.22C 1 [0.328 - ( 1-0.80 ) :.22C](1) = 0.2822
0.9 0.286 :.22C 1 [0.286 - ( 1-0.90 ) :.22C](1) = 0.2631
X A1 Az b Y/cm
0.3 0.115 :.13A 1 [0.115 - ( 1-0.30 ) :.13A](1) = 0.0184
0.4 0.123 :.13A 1 [0.123- ( 1-0.40 ) :.13A](1) = 0.0402
0.5 0.123 :.13A 1 [0.123 - ( 1-0.50 ) :.13A](1) = 0.0540
0.6 0.128 :.13A 1 [0.128 - ( 1-0.60 ) :.13A](1) = 0.0728
0.7 0.149 :.13A 1 [0.149- ( 1-0.70 ) :.13A](1) = 0.1076
0.8 0.184 :.13A 1 [0.184 - ( 1-0.80 ) :.13A](1) = 0.1812
0.9 0.289 :.13A 1 [0.289- ( 1-0.90 ) :.13A](1) = 0.2752
8. 4t K 7 <22.:nm
X A4 Az b Y/cm
0.3 0.503 :.;8A 1 [0.503 - ( 1-0.30 ) :.;8A](1) = 0.1194
0.4 0.498 :.;8A 1 [0.498 - ( 1-0.40 ) :.;8A](1) = 0.1692
0.5 0.474 :.;8A 1 [0.474 - ( 1-0.50 ) :.;8A](1) = 0.2240
0.6 0.459 :.;8A 1 [0.459 - ( 1-0.60 ) :.;8A](1) = 0.2398
0.7 0.436 :.;8A 1 [0.436 - ( 1-0.70 ) :.;8A](1) = 0.2716
0.8 0.361 :.;8A 1 [0.361 - ( 1-0.80 ) :.;8A](1) = 0.2514
0.9 0.185 :.;8A 1 [0.185 - ( 1-0.90 ) :.;8A](1) = 0.1302
;. 4 t K 7 <8:.:nm
X A5 Az b Y/cm
0.3 0.610 :.>2> 1 [0.610- ( 1-0.30 ) :.>2>](1) = 0.1011
0.4 0.585 :.>2> 1 [0.585- ( 1-0.40 ) :.>2>](1) = 0.1498
0.5 0.519 :.>2> 1 [0.519 - ( 1-0.50 ) :.>2>](1) = 0.1555
0.6 0.482 :.>2> 1 [0.482 - ( 1-0.60 ) :.>2>](1) = 0.1912
0.7 0.433 :.>2> 1 [0.433 - ( 1-0.70 ) :.>2>](1) = 0.2149
0.8 0.333 :.>2> 1 [0.333 - ( 1-0.80 ) :.>2>](1) = 0.1876
0.9 0.156 :.>2> 1 [0.156- ( 1-0.90 ) :.>2>](1) = 0.0833

From the graph .e plotted1
3nm D
ma!
3cm 5 *.hen D
ma!
+
;3:.: :.2A: :.C3;
;8;.: :.31; :.C3;
;>A.: :.2A> :.A3:
<22.: :.2>> :.<>:
<8:.: :.21; :.<C:
6alculate for the 'alues MnN at the specific 1
*a+ From the graph 7 ;3:.:- D
ma!
7 :.2A:cm- 5 7 :.C3;
"o - n 7 5
1-5
7 :.C3;
1-:.C3;
7 18.3A
O 18
Formula complex is i*en+
2
18$

*b+ From the graph 7 ;8;.:- D
ma!
7 :.31;cm- 5 7 :.C3;
n 7 :.C3;
1-:.C3;
7 18.3A
O 18
Formula complex is i*en+
2
18$

*c+ From the graph 7 ;>A.:- D
ma!
7 :.2A>cm- 5 7 :.A3:
n 7 :.A3:
1-:.A3:
7 8.AA
O ;
Formula complex is i*en+
2
;$

*d+ From the graph 7 <22.:- D
ma!
7 :.2>>cm- 5 7 :.<>:
n 7 :.<>:
1-:.<>:
7 2.:3:
O 2
Formula complex is i*en+
2
2$

*e+ From the graph 7 <8:.:- D
ma!
7 :.21;cm- 5 7 :.<C:
n 7 :.<C:
1-:.<C:
7 2.23
O 2
Formula complex is i*en+
2
2$

DI+C,++I"N :
From the experiment and the calculation that .e supposed to done- the 'alue MnN
should be obtain is 1- 2 and 3. ,t means the complexes .hich is attend is i *en+
2$
- i
*en+
2
2$
- and i *en+
3
2$
.This experiment sho. that .hen the 'alue of decrease- the mole
fraction*5+ .hen D*max+ increasing and .ill ma!e the n 'alue also increase. "o .hen n
decreasing- a complex compound .hich its ligand composition is big can be detected. 4t
lo.er .hich is ;3:.:nm and ;8;.:nm a complex compound that can be found is
i*en+
2$
. 9hile at 7;>A.:nm a complex compound that can be detected is i*en+
2
2$ .
4nd finally i*en+
2
2$
can be found at 7<22.:nm and <8:.:nm. The e0uilibrium
e0uation is as belo.1
i
2$
$ en i*en+
2$
2
1
*1a+
i*en+
2$
$ en i*en+
2
2$
2
2
*1b+
i*en+
2
2$
$ en i*en+
3
2$
2
3
*1c+
From this experiment .e obtained n 'alue 18 for both 7;3:.:nm and
;8;.:nm-n7; for 7;>A.:nm and n72 for both 7<22.:nm and <8;.:nm. 9e can see that
there a big n 'alue for 7;3:.:nm and ;8;.:nm This thing happen might because of an
error occurred .hile the experiment is being running and ma!e the n 'alue obtained
unacccurate.

The failures doing the experiment maybe because of the solution that .e
used are not pure enough. /espite of this- it also because of error in mix up the ligand-en
and nic!el. The 'olume of the mixture solution are not exactly 1:.: cm
3
. ,t may effect
ligand mole fraction and after that effect spectrum .e obtain and the absorbance 'alue-
4. The finger print may affect the absorbance 'alue become inaccurate .hen doing
experiment .ith spectrophotometer. "o to obtain the more accurate result some
precaution steps should be ta!en.
Pre*aution +tep:
1. Ma!e sure the all apparatus are used is clean and dry.
2. 6hoose the suitable and collect apparatus to a'id error .hen do the dilution.
3. "tirring the mixture to let it mix up together.
8. Ma!e sure the .all of tube is clean and dry.
;. Ma!e sure not finger print left on the tube to ensure UV result is not disturbed.
<. Ma!e sure not parallax exists .hen ta!ing the 'olume of the solution.
>. Ma!e sure the pure solution i
2$
and ligand *en+ are pure enough.
A. #nsure the tubes samples are .ash .ith sample solution before fill in the solution.

Con*lusion:
1. The Pob method is a easy and important method in determination of composition
of complexes by using the formula
n 7 5
1-5
so that the 'alue of n ligand *en+ .hich is bind to metal can be determine.
2. The absorption 'alues- 4
B
at ;3:.: nm- ;8;.: nm- ;>A.: nm- <22.: nm and
<8:.: nm respecti'ely is :.13A- :.1;1- :.22C- :.;8A and :.>2>.
3. The 'alue of n for each ;3:.: nm- ;8;.: nm- ;>A.: nm- <22.: nm and <8:
respecti'ely is 18-18-;-2 and 2


Referen*e:
1. "il'erstein- Q. M "il'erstein- Q. M- R.6. Lasster and T.6 Morrill *1CA1+
"pectrometric ,dentification of Irganic 6ompounds 8
th
#dition e. Dor! 1 John
9iley S "ons.
2. "!oog- Jolier- ieman- 1CCA Trincipal of ,nstumental 4nalysis Fifth #dition-
Jarcourt.
3. John 4. )andgrebe- 1CC3 Theory and Tractice in the Irganic )aboratory .ith
Microscale and "tandard "cale #xperiments 8
th
#dition Tacific Rro'e- 6alifornia.