Torrey Mullen

CHEM 4100
19th January 2011
Experiment 1

Hard and Soft Lewis Acids and Bases

Experimental Objective:
Synthesis and characterization of HgCo(SCN)4 and [Cu(thiourea)3(H2O)]2SO4 via acid base reactions with
the purpose of demonstrating the validity of the HSAB rule.

Introduction:
Acid base reactions are used to form a variety of salts and coordination complexes. They are one of the
most common reactions in inorganic chemistry. Acid base reactions can best be described in terms of
the Lewis definition of an acid and base. According to the Lewis definition, an acid is a substance that
can accept an electron pair and a base is a substance that donates an electron pair. With coordination
complexes, the central metal ion is a Lewis acid, and the ligands coordinated to the metal ion function as
Lewis bases. The stability of these coordination complexes varies greatly and depends on several factors.
A rule known as “The Principle of Hard and Soft Acids and Bases (HSAB)” is used to predict the formation
and stability of the wide range of complexes. The rule states that hard acids prefer to coordinate to hard
bases, and soft acids prefer to coordinate to soft bases. The terms soft and hard refer to the
polarizability of a cation or anion and are directly influenced by size. This means that a small anion or
base will form more stable complexes with cations or acids that are small also.

In the experiment, the validity of the HSAB principle will be observed through the formation of several
metal complexes using acid-base reactions. In part a, Co 2+ (hard acid) and Hg2+ (soft acid) is complexed to
SCN-, a bidentate ligand capable of acting as both a hard and soft base. In part b, Cu 2+ (hard acid), is
allowed to complex with thiourea (soft base).

Experimental procedure:
The experimental procedure was obtained: University of Wyoming Spring 2011 CHEM 4100 Lab Manual,
Experiment 1, pages 20-21.

Part (a): Synthesis of mercury cobalt tetrathiocyanate (HgCo(SCN)4)

Balanced equation:
Co(NO3)2* 6 H2O + 4 NH4SCN + HgCl2 HgCo(SCN)4 + 2 NH4Cl + 2 NH4NO3 + 6 H2O

Data:
Co(NO3)2*6H2O NH4SCN HgCl2 HgCo(SCN)4
molar mass (g mol-1) 291.07 76.13 271.49 491.84
mass initial (g) 0.995 1.266 1.019
mass final (g) 1.495
mmoles initial 3.42 1.66 3.75
mmoles final 3.04
mole ratio 1 4 1 1
Observations:
After mixing reagents and heating small, shiny, micro crystals began to form. After filtering the dense
microcrystalline solid were dark blue in color and had a metallic appearance.

Yield:
Theoretical yield: 3.42 mmol => (0.00342 mol) x (491.84 g mol-1) = 1.682 g
Yield of Product HgCo(SCN)4 : 1.495 g
Percent Yield = (actual/theoretical)*100% = (1.495g / 1.682g)*100% = 88.9%

Part B/C: Synthesis of Aquatris(thiourea)copper(I) sulfate ([Cu(thiourea) 3(H2O)]2SO4)

Balanced equation:
8 SC(NH2)2 + 2 CuSO4 * 5 H2O [Cu(SC(NH2)2)3(H2O)]2SO4*2H2O + [(NH2)2CSSC(NH2)2]SO4 + 6 H2O

Data:
SC(NH2)2 CuSO4*5H2O [Cu(thiourea)3(H2O)]2SO4
-1
molar mass (g mol ) 76.13 249.75 715.96
mass initial (g) 2.494 2.511
mass final (g) 2.861
mmoles initial 32.76 10.05
mmoles final 39.96
mole ratio 8 2 1

Observations:
Step B produced a precipitate that was flaky and yellowed white in color. After dissolution and
recrystallization the filtered product was fluffy and pure white in color.

Yield:
Theoretical Yield: 32.76 mmol = (0.03276 mol) x (1 mol / 8 mol) x (715.96 g mol -1) = 2.93 g
Yield of [Cu(thiourea)3(H2O)]2SO4: 2.86 g
Percent Yield = (actual/theoretical) )*100% = (2.86g / 2.93g)*100% = 97.6%

Discussion:
The synthesis of HgCo(SCN)4 and [Cu(thiourea)3(H2O)]2SO4 were each carried out following the
procedures described in the laboratory manual reference above. The isolated yield of 88.9% for
HgCo(SCN)4 and 97.6% for [Cu(thiourea)3(H2O)]2SO4 were very high. Loss of product was minimal due to
careful filtrations and recrystallization, though the loss came from these teps. The recrystallization of
[Cu(thiourea)3(H2O)]2SO4 was necessary to purify the product and involves dissolving the precipitate in a
hot, aqueous solution of thiourea. The excess thiourea and sulfate that remained undissolved was
filtered off, and the filtrate was cooled in an ice bath to allow the complex to crystallize out. The
solution was then filtered and washed. Infrared spectra for both compounds were measured as KBr
pellets, and data for the spectra is shown in the table below:

The spectrum of each compound is attached.

The HSAB involves acid-base reactions between hard and soft acids and bases. Soft acid and bases are
characterized as having high polarizability, that is, they contain electrons that can be easily distorted or
removed. Hard acids and bases have the opposite properties; they hold on to their electrons much
more tightly and have low polarizability. The HSAB concept states that hard acids prefer to coordinate
to hard bases, and soft acids prefer to coordinate to soft bases.

In this experiment, the bidentate ligand SCN - acts as a hard base when coordinated through the
nitrogen, and a soft base when coordinated through the sulfur. Such was the case when the ligand was
coordinated to Co2+ and Hg2+, a hard and soft acid, respectively. The ligand adheres to the HSAB
principle, acting as a soft base and coordinating to the Hg 2+ through S, and acting as a hard base and
coordinating to the Co2+ through N. The resulting complex contains both Co and Hg with tetrahedral
geometries bound together through the SCN ligand.

In the case of the [Cu(thiourea)3(H2O)]2SO4 complex, thiourea is a soft base, and the Cu 2+ reagent is a
borderline hard-soft acid. During the synthesis, the Cu 2+ ion undergoes a redox process to form Cu 1+, a
soft acid that allows for a more stable complex to be formed with the soft base thiourea. Water, a
strong base, coordinates to the Cu to fulfill a tetrahedral shape. The resulting complex has an overall
charge of 1+, and forms a salt with the SO 42- in solution.

References:

Bott, R.; Bowmaker, G.; Davis, C.; Hope, G.; Jones, B., Inorganic Chemistry 1998, 37,651-657

Shriver, D.; Atkins, P., Inorganic Chemistry, 3rd Ed., W.H. Freeman and Co., NY, 2003, pp 167-169