I. Chemical Equilibrium: I.1-Coordination Chemistry: Nickel Complexes
I. Chemical Equilibrium: I.1-Coordination Chemistry: Nickel Complexes
The experiments described in these materials are potentially hazardous and require a high
level of safety training, special facilities and equipment, and supervision by appropriate
individuals. You bear the sole responsibility, liability, and risk for the implementation of
such safety procedures and measures. MIT shall have no responsibility, liability, or risk for
the content or implementation of any of the material presented.
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I. Chemical Equilibrium
2+
OH2
H2O
Ni
H2O
H2O
2+
OH2
OH2
OH2
-2H2O
N
Ni
N
OH2
OH2
H2O
Further additions of ethylenediamine form the di- and tri- ethylenediamine complex, which have
geometric and/or optical isomers.
2+
N
N
N
Ni
OH2
H2O
2+
OH2
N
Ni
N
OH2
OH2
H2O
2+
N
N
N
Ni
2+
N
N
N
N
Ni
N
OH2
H2O
-2H2O
Materials:
2 mL of 1.0 M Nickel sulfate (NiSO4) solution
Discussion:
- Draw the missing isomers in the Background section and describe in each case the type of
isomerism.
- At approximately what wavelengths of the electromagnetic spectrum do these complexes,
[Ni(H2O)6]2+, [Ni(H2O)4(en)]2+, [Ni(H2O)2(en)2]2+, [Ni (en)3]2+, absorb light?
- Use your understanding of the splitting of d orbitals and the spectrochemical series to explain
your results.
The equilibrium constant for this reaction, or solubility product, Ksp, is given by:
Ksp = [Ag+][Cl-].
A simple relation exists between the solubility of an ionic compound (S) and its solubility
product:
Ksp = S2
It can be easily shown that for the general solubility equilibrium
m+
n
The formation of coordination complexes can have a large effect on the solubility of a compound
in water. Silver chloride is only very weakly soluble in water, but addition of ammonia (NH3) to
the solution allows the complex ion Ag(NH3)2+ to form:
+
Materials:
1.0 mL of 0.1M silver nitrate (AgNO3)
50mL beaker
Safety: Sulfide salts, their solutions and hydrogen sulfide gas, which smells like rotten eggs at
low concentration and is produced by reaction of sulfides with acids, are all poisonous. Avoid
adding any acid to a solution containing sulfide salts. Silver nitrate solutions are light sensitive,
irritating and oxidizing. Ammonium hydroxide is corrosive and highly irritating upon inhalation.
Procedure:
- Place a 50mL beaker containing 20 mL of distilled water and a magnetic stirring bar on the
magnetic stirrer, and adjust the rate of stirring so it is vigorous but not turbulent.
- Add about 1 mL of AgNO3 solution and allow time for complete mixing.
- Add dropwise in sequence the following solutions until a change is clearly observed. This
will generally be 0.5-1.0 mL (10-20 drops): NaHCO3, NaOH, NaCl, NH3, NaBr, Na2S2O3,
KI, and Na2S.
- Write down your observations (color, state, etc.).
HCO 3
NH 3
OH
Cl
Ag + (aq)
Ag2 CO3 (s)
Ag2 O(s)
AgCl(s)
Ag( NH3 )2
+
S 2 O32
Br
3 2
3
S 2
I
AgI(s)
Ag2 S(s)
Clean Up: Precipitate any silver still in solution by adding excess sodium sulfide.
Discussion: Silver forms a series of precipitates and complex ions with different solubilities and
formation constants, respectively.
Interpret your results in terms of solubility constants, complex formation constants, and relative
concentrations of reactants. How could you explain the different solubilities of the silver
halides?
Compound
Ksp
Ag2CO3
6.2x10-12
AgOH
1.5x10-8
AgCl
1.6x10-10
AgBr
7.7x10-13
AgI
1.5x10-16
Ag2S
6.3x10-51
Kf
[Ag(NH3)2]+
1.7x107
[Ag(S2O3)2]3
2.9x1013
R T2 T1
where H is the change in enthalpy of the reaction, R the universal gas constant (8.31 J K-1mol
1
), and K1 and K2 , the equilibrium constants at temperatures T1 and T2, respectively.
Materials:
0.5g cobalt(II) chloride hexahydrate, CoCl26H2O
12 mL 2-propanol, C3H7OH
distilled water
Test tube with stopper
Hot water bath
ice-salt bath
Safety: Cobalt chloride is a suspected carcinogen in animals. The dust is a respiratory tract
irritant. Isopropanol is a flammable liquid and vapor (may cause a flash fire). REMOVE stopper
before heating (never heat a closed system). When heating the testtube be sure it is not pointed
towards yourself or colleagues.
Procedure:
- Place 0.5g of CoCl26H2O in a large test tube
- Add 12 mL of 2-propanol
- Stopper and shake to dissolve solid. Note the color of the solution.
- Carefully add water dropwise, with mixing, until a color change is observed.
- Place the unstoppered test tube in a boiling water bath. Observed any color change.
- Transfer the test tube to an ice bath. Record your observations.
Clean up: Discard the cobalt solution in the designated containers.
Discussion: Identify the colored species.
principle.
2 propanol
H2
CoCl2 (s) CoCl42
Co(H2 O)6
2+
+ heat
Consider the solubility of AgCl. What is the concentration of Ag in a saturated solution (i.e., there is
solid present)?
+
initial
change
equilibrium
-
solid
0
0
+x
+x
+x
+x
-10
-5
x= [Ag ] = [ Cl ]= 1.3 x 10 M
The concentrations of the ions are very low in aqueous solution and whenever the concentrations
-5
of the ions exceeds 1.3 x 10 M precipitation occurs and consequently unreacted silver halide is
not readily removed by simple washing.
How to remove unwanted AgCl from the image?
+
32Ag (aq) + 2 S2O3 (aq) [Ag(S2O3)2] (aq)
3-
Kf = [[Ag(S2O3)2] ]
+
very soluble
Combine reactions:
+
AgCl (s) Ag (aq)
+
2-
+ Cl (aq)
2- 2
[Ag ][ S2O3 ]
Ksp
3-
(aq)
3-
Kf
-
(aq) + Cl (aq)
Krxn = Ksp x Kf
Coupling of two reactions permits pulling AgCl solid into solution and with sufficient washing in water
to remove the products, the light sensitive silver halide is removed from the photographic image. In
reality there is a variety of soluble silver thiosulfate complexes formed.
To prepare a negative to be used for obtaining a cyanotype print later in the course a Polaroid Land
camera and Polaroid Polapan 665P/N will be used. The chief advantage of this route to obtaining a
negative is no darkroom is required to obtain a printable negative.
Materials:
Polaroid 220 Land Camera
Polapan 665P/N (Polaroid Black and White Positive/Negative Instant Pack Film)
Sodium sulfite solution
Safety: Wear gloves when separating the film pack as the proprietary chemical mixture is
caustic.
Procedure:
You will be given instruction on use of the camera to obtain an image and on the procedure for
developing the instant pack film. The negatives are washed in a sodium sulfite solution and
rinsed in water. A final rinse in a proprietary surfactant solution is used to minimize water
spotting on the negative prior to hanging the negative to dry. To protect the positive image, the
black and white print must be coated with the coater provided with the film.
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