102 Lab 12 KF FeSCN Complex Ion Sp19
102 Lab 12 KF FeSCN Complex Ion Sp19
102 Lab 12 KF FeSCN Complex Ion Sp19
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.
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 expression for the formation constant, Kf, with aqua ligands omitted for simplicity is:
[Fe(SCN )n3−n ]
K = (4)
f [Fe 3+ ][SCN − ]n
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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.
[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.
[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:
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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?
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.
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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)
Experimental Data
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.
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E14 Spectrophotometric Determination of an
Equilibrium Constant, Kf
Report Form
− K f )2
=∑ ∑(K
K f fi
Kf = σ= =
n n −1
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