Experiment 10: A Study of the Equilibrium between Ferric and

Thiocyanate Ions

Aim:
To measure the equilibrium constant for the reaction:
Fe(aq)
3+
+ nSCN
-
Fe(SCN)
n
(aq)
(3-n)+
And to confirm that for the given experiment conditions the value of n is unity.
Introduction:
The Equilibrium constant, K of the reaction forming the complex ion Fe(SCN)(aq)
2+
can be
determined through the application of Beers Law:
A=bm
From measuring the absorbance, the final concentration of the complex can be found and by
graphing the inverse of the Fe
3+
concentration against the inverse of the absorbance, the K value can
be determined and compared the literature data K values.
Procedure:
The experimental was conducted using the method outlined in the 123.201 Chemical Energetics:
Laboratory Manual. No deviations were made from this method. The sample preparation was
divided between the two members of the lab group. Jessica Arthur prepared samples G-L and I
prepared samples A-F.
Results
Wavelength of the Maximum Absorbance of Sample A=458.0nm
Ionic Strength =m
i
z
i
2
=((0.3*3
2
)+(0.3*(-3)
2
)+(0.010*(-1)
2
)+(0.010*1
2
)+(1.0*1
2
)+(1.0*(-1)
2
)+(1.0*(-1)
2
))
=4.21mol dm
-3
The final concentrations of Fe
3+
and SCN
-
were calculated using the equation:
C
1
V
1
=C
2
V
2
Solution 0.30M
Fe
3+
/cm
3
0.010M SCN
-
/cm
3
Final
Concentration
Fe
3+
mol/L
Final
Concentration
SCN
-
mol/L

Absorbance
A 0.6 2.4 0.0036 0.00048 0.525
B 0.6 2.0 0.0036 0.0004 0.455
C 0.6 1.6 0.0036 0.00032 0.359
D 0.6 1.2 0.0036 0.00024 0.271
E 0.6 0.8 0.0036 0.00016 0.180
F 0.6 0.4 0.0036 0.00008 0.078
G 4.0 1.0 0.024 0.0002 0.545
H 2.0 1.0 0.012 0.0002 0.428
I 1.2 1.0 0.0072 0.0002 0.337
J 0.8 1.0 0.0048 0.0002 0.263
K 0.6 1.0 0.0036 0.0002 0.213
L 0.4 1.0 0.0024 0.0002 0.160

Solution 1/Absorbance 1/Final Concentration Fe
3+

L/mol
A 2.188183807 277.777778
B 2.512562814 277.777778
C 3.246753247 277.777778
D 4.545454545 277.777778
E 6.944444444 277.777778
F 14.70588235 277.777778
G 1.945525292 41.6666667
H 2.512562814 83.3333333
I 3.333333333 138.888889
J 4.405286344 208.333333
K 5.376344086 277.777778
L 7.407407407 416.666667

Slope Intercept
Value 0.014625511 1.319561
Error 8.60197E-05 0.019932
R
2
0.999861652
Degree of Freedom 4
s(y) 0.026554
F 28908.56976
Regression Sum of Squares 20.38374828
Residual Sum of Squares 0.00282

The equilibrium constant was determined using the slope and the intercept of Figure 2 in:
K=intercept/slope
K=0.014625511/1.319561
K=90.22321
The Standard Error of the K value:
K
ERROR
= (intercept0.019932/slope8.60197E-05)-K
K
ERROR
=(0.0146255110.019932/1.3195618.60197E-05)-90.22321
K
ERROR
=92.12787-90.22321
K
ERROR
= 1.904663

K=90.221.90

Figure 1: The absorbance of solutions A-F was plotted as a function of the Final Concentration of
SCN
-


Figure 2: The inverse of the absorbance of solutions A-F was plotted as a function of the inverse of
the Final Concentration of Fe
3+


y = 998.21x - 0.0137
R = 0.9976
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006
A
b
s
o
r
b
a
n
c
e

Final Conc SCN(-1) mol/L
Solutions A-F
A-F
Linear (A-F)
y = 0.0146x + 1.3196
R = 0.9999
0
1
2
3
4
5
6
7
8
0 100 200 300 400 500
1
/
A
b
s
o
r
b
a
n
c
e

1/Fe(3+) L/mol
Solutions G-L
G-L
Linear (G-L)
Discussion
The experimental value of K at a temperature of 24C and an ionic strength of 4.21, was calculated
to be 90.221.90. The R
2
value of figure 2 (0.9999) is an acceptable value indicating that there was
minimal deviation of the experimental result from the theoretical result based on the linear model.
This is also confirmed visually by the points being on or very near the linear model line. K value
obtained from the literature data was log (2.1) or 125.89. This was at a temperature of 25C and the
ionic strength was not stated. This is not within the range of the experimental K value. This
significant difference could be attributed to the incorrect handling and cleaning of the curvette,
where fingerprints or tissue marks can cause fake readings. Also too much or too little solution will
cause the spectrophotometer to fluctuate as the light passes through the solution. There may have
also been a change in temperature as rooms were changed which will impact the K value. Other
minimal sources of error could be during the preparation of the stock solutions and the purity of the
reagents used, as well as dirty equipment during the experiment.
The equilibrium was not studied under constant ionic strength. The ionic strength of 4.21 was not
significantly high. A high ionic strength indicates high chemical activity, which means the reaction is
not displaying the ideal behaviour.
HNO
3
is added to the 0.30moldm
-3
Fe(NO
3
)
3
solution to stabilize the Fe
3+
ion, as Fe ions prefers to be
in the lower energy state of Fe
2+
. If water was added instead then the complex ion, [Fe(H
2
O)
5
OH]
2+

(a strong cation) would form preventing Fe(SCN)
3
from forming.
[Fe(H
2
O)
6
]
3+
+ H
2
O [Fe(H
2
O)
5
OH]
2+
+ H
3
O
+

Conclusion
Through the use of a spectrophotometer and the application of Beers Law, the equilibrium constant,
K was determined to be 90.221.90 In Excel a linear regression the line of best fit, y=0.0146x+1.3196
and the R
2
value of 0.9999 were found. Although the R
2
value is close to 1, it does not mean the
resulting data would be representative of the literature data K value. This was found to be 125.89,
which is significantly different from the experimental K value. The value of n was confirmed to be
unity. It is recommended that possible sources of errors be determined and this experiment be
repeated.