Finding the Equilibrium Constant for a Reaction

Valentin Uzunov (author) & Francesca Frattaroli (lab partner)

PSU ID#: 964100377
CHM 228H (Lab 261), Due: 3/14/2014

ABSTRACT
The objective of the experiment was to calculate the equilibrium constant for the reaction of iron
(III) and thiocyanate at room temperature (21 C). The absorbance of 4 different solution
mixtures and 1 standard solution were measured at equilibrium using a spectrometer. From the
absorbance and concentrations of the standards, the concentrations of the reactants and product (
thiocyanoiron(III) complex) were determined using Beer-Lamberts law. The equilibrium constant was
calculated by substituting the respective concentrations into the equilibrium constant expression for the
reaction. The average equilibrium constant for all trials was determined to be 85.31 4.30 (2sd), which
compared to aggregate results of 138.19 103.86 (2sd), was a 61.7% difference.

INTRODUCTION
When a chemical reaction takes place, typically the reaction does not go to completion, rather the system
arrives at an intermediate state where the concentrations of the reactants and products no longer change
with time. At this state the rate of the forward reaction is equal to the rate of the reverse reaction and the
system is said to be in dynamic equilibrium. For a general chemical system in equilibrium at 298K such
as:
aA + bB cC + dD [Rxn 1]
Setting the rates of the forward and reverse reactions equal and rearranging the equations, leads to the
following expression:

[]

[]

[]

[]

[Eq 1]
where

is the ratio between the rate constants of the forward and reverse reaction, a constant value at
fixed temperature and pressure. The notation []

represents the initial molar concentrations of the

chemical species, the exponents are the respective reagent orders, and K
c
is the equilibrium constant.
Guldberg and Waage in 1864, were the first to propose a relationship between the balanced chemical
equation and the equilibrium constant, this relationship is known as the law of mass action. The law of
mass action defines the K
c
for the system as the ratio of the product concentrations to reactant
concentrations, at the equilibrium point:

[]

[]

[]

[]

[Eq 2]
Where the notation []

now represents molar concentration of the chemical species in their standard

states at equilibrium, and the exponents are the respecting stoichiometric coefficients from the balanced
equation.
The purpose of this experiment was to measure the equilibrium constant for the reaction between iron(III)
nitrate [Fe(NO
3
)
3
] and potassium thiocyanate [KSCN] producing thiocyanoiron(III) [FeSCN
2+
] complex:
Fe3+ (aq) + SNC- (aq) FeSCN
2+
(aq)

[Rxn 2]
From the equilibrium concentration of thiocyanoiron(III) [FeSCN
2+
] the equilibrium concentrations of all
the other interacting species were determined, and used to calculate the K
c
.
The equilibrium concentration of Fe(SCN)
2+
was determined using Absorbance Spectroscopy which
involves measuring the intensity of light after it passes through a colored solution, with a Spectrometer.
The deeper the color, the more light that will be absorbed. This relationship direct relationship between
absorbance and concentration is known as Beer-Lamberts Law, which states that, the quantity of light
absorbed by a substance dissolved in a nonabsorbent solvent (such as the water) is directly proportional to
the concentration of the substance and the path length of light through the solution, given by the
expression:

[Eq 3]
Where A

in this case is the measured absorbance of the Fe(SCN)

2+
complex, whose formation is
responsible for the dark red color of the solution, l is the light path length, determined by the length of the
cuvette containing the reaction, and is the excitation coefficient of the solution which quantifies the
ability of a molecule to absorb light at the given wavelength. The influence of any unreacted SCN- and or
Fe3+ on the measurement was believed to be negligible, as SCN- and or Fe3+ solution at dilute
concentrations are weakly colored. Once the equilibrium concentration of the Fe(SCN)
2+
was determined,
the equilibrium concentrations of the reagents was determined from stoichiometry of the [Rnx 2], and
subsequently the K
c
was calculated from [Eq 2]
Ideally the K
c
determined should be constant for all trials, however some deviation was expected. The
only means to test the validity of the results is to compare the current results with the aggregate. A large
difference or large standard deviations in the final K
c
determine would invalidate both sets of data. A
large K
c
value is expected.

DATA
Table 1 Shows absorbance data at different concentrations of SCN
-
at 21C. Absorbance for wavelength of 450 nm
Trial
Fe(NO
3
)
3

(mL)
KSCN
(mL)
H
2
O
(mL)
Initial Concentrations
Absorbance
Fe
3+
SCN
-

1 5 2 3 0.001 0.0004 0.18
2 5 3 2 0.001 0.0006 0.252
3 5 4 1 0.001 0.0008 0.34
4 5 5 0 0.001 0.001 0.42
5
(standard)
18 2 0 0.18 0.0002 1.146







Table 2 - Aggregate data for all trials at room temperature
(

)
(of standard)
Trial 1 K
c
Trial 2 K
c
Trial 3 K
c
Trial 4 K
c
K
c
Mean K
c
STD
5730 87.991 82.735 85.1667 85.352 85.311 2.148
3300 23.569 18.398 11.619 8.600 15.546 6.737
5035 65.399 89.372 121.970 86.931 90.918 23.336
3765 96.166 102.315 108.320 108.683 103.871 5.909
3350 74.400 116.100 120.400 121.300 108.050 22.548
3860 367.605 776.725 245.149 327.283 429.190 237.227
2760 170.330 168.350 143.170 167.550 162.350 12.840
3505 131.033 129.382 131.553 120.670 128.159 5.078
4000 132.730 124.030 144.070 134.960 133.948 8.233
2650 139.000 143.400 144.000 142.800 142.300 2.254
2540 130.000 120.000 118.75 113.000 120.438 7.066


RESULTS & DISCUSSION
Table 3- Concentrations of reactants and products at equilibrium for reaction between Fe
3+
, SCN
-
and FeSCN
2+
at 21C
Trial [ Fe
3+
] [ SCN
-
] [ FeSCN
2+
] K
c


1 0.000969 0.000369 0.0000314 87.991
2 0.000956 0.000556 0.0000440 82.735
3 0.000941 0.000741 0.0000593 85.167
4 0.000927 0.000927 0.0000733 85.352
5 (standard) 0.180 0.000 0.000200 0 5730

The results from Table 3 show the mean equilibrium constant (K
c
) for the reaction between
iron(III) and thiocyanate was 85.31 4.30 (2sd). Given the current results and standard
divination achieved, it is fair to presume that with improved experimental procedures it would be
expected that the K
c
values measured will converge onto a constant value. In contrast, the mean
value determined from the aggregate results was 138.19 103.86 (2sd), which was a 61.7%
difference. Given the large standard deviation of the aggregate results it would not be possible to
justifiably ascertain that the K
c
value is constant.
The measured equilibrium constant should be the same for a given temperature, regardless of
initial concentrations [1], however this is not accurately portrayed in either set of data. It is
possible that a systematic error was introduced into the current results due by potentially not
allowing the solutions sufficient time to reach equilibrium before measuring the absorbance. This
would lead to a systematic decreased absorbance values and systematically low K
c
values.
Alternatively an error could have been made in the preparation of the standard or in the
recording/measurement of the absorbance of the standard solution. An inaccurately high
absorbance value would introduce a systematic bias in subsequent calculations which would also
cause the determined K
c
values to be systematically low, alternatively if the absorbance of the
standard was actually lower than that recorded, the K
c
values determined would have been
systematically higher and closer in agreement to the aggregate results. Without more trials and
repeated experimental results it is difficult to determine if an error had been made, and where.
Further investigation is required.

CITATIONS
1- Tro, Nivaldo J.Chemistry: A Molecular Approach. Upper Saddle River, NJ: Pearson Prentice
Hall, 2011. Print.

CALCULATIONS