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Assignment 1: due in the class on 16 Jan 2018

1. The mean activity coecients of KCl in three dilute aqueous solutions at 25°C are 0.927 (at 5.0 mmol kg−1 ),
0.902 (at 10.0 mmol kg−1 ), and 0.816 (at 50.0 mmol kg−1 ). Estimate the value of B in the extended Debye-
Hückel law.
Ans.

2. The addition of a small amount of a salt, such as (NH4 )2 SO4 to a solution containing a charged protein
increases the solubility of the protein in water. This observation is called the salting-in eect. However,
the addition of large amounts of salt can decrease the solubility of the protein to such an extent that the
protein precipitates from solution. This observation is called the salting-out eect and is used widely by
biochemists to isolate and purify proteins. Consider the equilibrium PXν (s)
Pν+ (aq) + ν X− (aq), where
Pν+ is a polycationic protein and X− is its counter ion. Use Le Chatelier's principle and the physical principles
behind the Debye-Hückel theory to provide a molecular interpretation for the salting-in and salting-out eects.

3. The mean activity coecients for aqueous solutions of NaCl at 25°C are given below. Conrm that they
support the Debye-Hückel limiting law and that an improved t is obtained with the extended law.

b/(mmol kg−1 ) 1.0 2.0 5.0 10.0 20.0


γ± 0.9649 0.9519 0.9275 0.9024 0.8712

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