E14 Chemical Equilibria: Spectrophotometric

Determination of a Formation constant, Kf.

Objective

! To determine the stoichiometry of the complex ion formed between iron(III) ion and thiocyanate
ion by the method of continuous variation (MCV), Job’s method.
! To prepare a standard curve (Beer-Lambert plot) of the absorbance of an iron-thiocyanate
complex ion versus its concentration. This will be used to determine the concentration of the
complex ion formed at equilibrium.
! Determine the value of the formation constant, Kf, from the concentrations of reactants and
product in each equilibrium samples measured.

Introduction
As you have encountered in previous experiments molecular association is the basis of simple acid-base
equilibria, metal ion solvation, transition metal coordination, and dissolution among others. In this
experiment we will learn a method by which the stoichiometry of such association is detected. A classic
paper published by Paul Job in 1928 showed that plotting UV absorption versus mole fraction, XA, of
Tl(NO3) in Tl(NO3)/NH3 mixtures resulted in a plot similar to the idealized depiction in Figure 1.

A maximum in the curve at χ = 0.5 revealing a 1:1 molecular association. The graphical output of what
had previously been referred to as the method of continuous
variations (MCV) became synonymous with a Job plot.

TlNO3 + NH3 ! H3N−TlNO3 (1)

In our experiment we are interested in the stoichiometry of

association between Fe3+(aq) and SCN-(aq) ion to form the complex
ion Fe(SCN)n3-n represented symbolically (Eq’n 2) with A and B.

Kf
A + nB ! ABn (2)

By the MCV the total concentration of added Fe3+(aq) and Figure 1. Job plot obtained from a 1:1
SCN-(aq) are held constant and vary the relative proportions association displaying a maximum in
of A and B. The units on the x axis are changed from physical property, P, at mole fraction of
A, XA, of 0.5 (Eq 1).
concentrations to mole fraction of χA and χB
(χA or χB such that χA = [A]/{[A]+[B]} = 1-χB ). The use of mole
fraction or its equivalent along the x-axis is shared by all Job plots.
The most common dependent variable on the y-axis is the absorbance, but any property that correlates
linearly with the concentration of the product, ABn suffices, including but not limited to, mass of a
precipitate, and rate constants.
Job plots corresponding to binary 1:1 associations using normalized Absorbance as physical property, P,
with equilibrium (formation) constants, Keq=1, Keq=10, and Keq=100 is given in Figure 2 below.
In Figure 3 is a Job plot showing the prevalent 2:1 association AB2.
 Formation Constant, Kf

Figure 2. Job plot derived from a 1:1 complex Figure 3. Job plot derived from a 2:1 complex

The shape of the curve provides qualitative insight into Kf (Figure 2). Strong binding (Kf > > 1) affords
a more angular plot approaching the shape of a perfect triangle in the limit, whereas an equilibrium with
Kf ∼ 1 more balanced equilibrium affords gentle curvature. The position of the maximum at χA=0.5,
identified by the maximum along the y-axis (or by inspection for the simplest analyses), provides the 1:1
stoichiometry of an AmBn complex (m=n). The position of the maximum does not distinguish 1:1, 2:2,
and other m:m relative stoichiometries, but subtle changes in curvature can provide clues of higher
order complexes. The Job plot displaying a maximum at χA=0.33 (Figure 3) are prevalent.

The Iron(III)-Thiocyanate Complex

In solution Fe3+ ion reacts with thiocyanate ion, SCN-, to form a complex ion according to equation 3.

Fe(H2O)63+(aq) + nSCN-(aq) ! Fe(H2O)6-n(SCN)n3-n + nH2O (3)

The expression for the formation constant, Kf, with aqua ligands omitted for simplicity is:

[Fe(SCN )n3−n ]
K = (4)
f [Fe 3+ ][SCN − ]n

A. Preparation of a Beer-Lambert’s Law Plot

Review the Beer’s Law relationship between Absorbance and Concentration given in experiment
2 (E2) Part 3.
Prepare a stock solution of Fe(H2O)6-n(SCN)n3-n by Table 1. Stock Sol’n 0.10 M Sol’n
taking 1.00 mL of 0.00200 M Fe(NO3)3 solution (mL) (mL)
and dilute to 25.00 mL with 0.10 M KSCN. The high Tube No. Fe(SCN)n 3-n
KSCN
[SCN-] concentration guarantees that virtually all of 1 4.00 0
the iron in the solution is in the form of the complex- 2 3.00 1.00
ion. Use a Mohr pipet to measure the solution 3 2.00 2.00
volumes very accurately! Set up the following 4 1.00 3.00
standard solutions from the stock solution and 0.10 M 5 Blank - ~3
KSCN as in Table 1.

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 Formation Constant, Kf
Cover each standard dilution test tube with parafilm to avoid evaporation. All samples will be read
together on the spectrophotometer following the preparation of the equilibrium samples.

The concentration of Fe(SCN)n3-n in the stock solution is

[Fe(SCN)n3-n] =(1.00/25.00)(0.00200 M)= 8.00 x 10-5 M
3-n
The Fe(SCN)n concentration of the standards are calculated similarly:

[Fe(SCN)n3-n]1=8.0 x 10-5 M; [Fe(SCN)n3-n]2=(3.00 mL/4.00 mL)8.0 x 10-5 M=6.0 x 10-5 M, see below.

B. Preparation of Equilibrium samples using Continuous Variation of Reactants

By preparing equilibrium samples in which one reactant increases systematically while the other
decreases we will be able to find the stoichiometry of the complex-ion that gives the greatest
absorbance. Don’t forget to cover each equilibrium sample dilution with parafilm to avoid evaporation.
Set up the equilibrium samples (cover test tubes with parafilm) as follows:

Table 2. 0.00200 M 0.00200 M

Solutions Solutions
(mL) (mL)
Tube No. Fe3+ KSCN
1 0 10
2 2 8
3 4 6
4 5 5
5 6 4
6 8 2
7 10 0
Note that Tube No. 1 and 7 do not have to be filled. Complex ion formation is not possible since one of
the reactants is missing.
When all the solutions have been prepared measure and record the %Transmittance of each solution at
450 nm. You will need two spectrophotometer cuvettes for your analysis, one for the blank to calibrate
the instrument and one for reading all the samples.
For the standard solutions calibrate the spectrophotometer with 0.10 M SCN- solution (%T=100).
For the equilibrium samples calibrate the spectrophotometer with 0.0020 M SCN- solution (%T=100).
Read and record the percent transmittance (%T) of each solution and calculate the absorbance from
A=2 – log(%T). {Show your recorded data to your instructor for approval.}

C. Calculations and Results

1. For the standard curve calculate the [Fe(SCN)n3-n] in each standard according to:

[Fe(SCN)n3-n]tube(n)=(V(Stock)/Vtotal)(8.0 x 10-5 M)

Plot Absorbance versus [Fe(SCN)n3-n]. Obtain the trendline and R2(correlation coefficient). Use the
trendline and the Absorbance (obtained from %T) of the equilibrium samples to determine the
concentration of [Fe(SCN)n3-n] in the equilibrium samples.

2. For the equilibrium samples plot the Absorbance versus mol fraction Fe3+ added. Since both
reactants have the same concentration the mol fraction of each component is equal to the volume of
Fe3+ or SCN- used divided by the total volume.

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 Formation Constant, Kf
nfe MVFe VFe
χFe = = =
nFe + nSCN MVFe + MVSCN VFe + VSCN

Have Excel draw a smooth curve through the data points. Determine the stoichiometry between Fe3+
and SCN- from the 3+
€ peak of absorbance versus mol fraction of Fe added.
Example: If your peak occurs at χ=0.20 Fe then this corresponds to χ=0.80 SCN-.
3+

This gives a ratio of SCN-/Fe3+ =4/1 and corresponds to a complex ion => Fe(SCN)4-(aq).
Once you have determined the correct stoichiometry the concentration of the species that go into
your expression for the formation constant are:

(a) [Fe-SCN-complex]eq =(A – b)/m, where A=absorbance, b=intercept, m=slope.

(b) [Fe3+]eq=[Fe3+]o - [Fe-SCN-complex]eq, [SCN-]eq=[SCN-]o - n[Fe-SCN-complex]eq
(c) Calculate Kf from equilibrium samples 2-6.
(d) Determine the average value of Kf, and
(e) Calculate the standard deviation Kf.

[Fe − SCN − cplx]eq

Kf =
[Fe 3+ ]eq [SCN − ]eq
n

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 E14 Spectrophotometric Determination of an
Equilibrium Constant, Kf
Report Form
Name: ____________________ Partner’s Name: __________________(if any)_Lab Section: MW/TTH/M-TH/F
(circle)
Advanced Study: Pre-Laboratory Assignment

1. When applying the method of continuous variation (MCV) what values are held constant?
What is/are being varied?

2. How is the stoichiometry between the reactants determined from the plot?

3. What physical property are we plotting on the y-axis? _______________________

4. How does the dependent variable, Absorbance, correlate with the complex ion formed in the
reaction? __________________________.

5. Show how you obtain the concentration of the complex ion, [Fe(SCN)n3-n], in standard tube No. 4.

6. On the spectrophotometer, E200, we will be recording the __________________

at the wavelength, λ= ______________nm.

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 E14
Name: ____________________
Experimental Data
Spectrophotometric Determination of an
Equilibrium Constant, Kf
Report Form
Partner’s Name: __________________(if any)_Lab Section: MW/TTH/M-TH/F
(circle)

1. Concentration of the Fe(NO3)3(aq) used to prepare the stock solution of Fe(SCN)n3-n = __________M.

2. Concentration of the KSCN(aq) used to prepare the stock solution of Fe(SCN)n3-n = __________M.

3. %T Data for Beer-Lambert Plot

Table 3. Stock Sol’n 0.10 M Sol’n

(mL) (mL)
3-n
Tube No. Fe(SCN)n KSCN [Fe(SCN)n3-n] %T Absorbance
M
1 4.00 0
2 3.00 1.00
3 2.00 2.00
4 1.00 3.00
5 Blank - ~3 100 0

Trendline from Beer-Lambert Plot (A vs. [Fe(SCN)n3-n])=__________________________________

4. %T Data for Equilibriated Samples

Table 4. 0.00200 M 0.00200 M

Solutions Solutions
(mL) (mL)
Tube No. Fe3+ KSCN %T Absorbance
1 Blank 0 10 100 0
2 2 8
3 4 6
4 5 5
5 6 4
6 8 2
7 10 0 100 0

Attach your Beer’s Law and Continuous Variation plots to report.

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 E14 Spectrophotometric Determination of an
Equilibrium Constant, Kf
Report Form

5. Calculations of Equilibrium Concentrations and Kfs.

Show calculations for each component of the equilibria in tubes 2-6.

Tube 2. [Fe(SCN)n3-n]eq= Kf=

[Fe3+]eq = [SCN-]eq=

Tube 3. [Fe(SCN)n3-n]eq= Kf=

[Fe3+]eq = -
[SCN ]eq=

Tube 4. [Fe(SCN)n3-n]eq= Kf=

[Fe3+]eq = [SCN-]eq=

Tube 5. [Fe(SCN)n3-n]eq= Kf=

[Fe3+]eq = -
[SCN ]eq=

Tube 6. [Fe(SCN)n3-n]eq= Kf=

[Fe3+]eq = [SCN-]eq=

6. Enter Equilibrium Data in Table Below.

Tube [Fe3+]eq M [SCN-]eq M [Fe(SCN)n3-n]eq M Kf

No.
2

− K f )2
=∑ ∑(K
K f fi
Kf = σ= =
n n −1

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