Physical Biochemistry Module Workshop 1 Solution Chemistry (1) ANSWERS

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1) You are working for a biotechnology company and are measuring the complexation of a drug with a natural protein; the complexation process is associated with the biological activity of the drug. The reaction follows the equation [Drug] + [Protein] [Complex]

a) Write the equation for the equilibrium constant K for this reaction

K=
b)

[ Complex] [ Drug ][ Pr otein]

You look up your lecture notes and see that the equilibrium constant can be related to the standard Gibbs free energy of the reaction via G o = RT ln K

Your notes also state that this equation can be combined with the Gibbs equation to yield the vant Hoff equation ln K = Show that this is the case You know G o = RT ln K Substituting for Go yields RT ln K = H o TS o Making lnK the subject of the equation by dividing through by RT gives the vant Hoff equation G 0 = H 0 TS 0 H 0 S 0 + RT R

c)

You measure the equilibrium constant at a range of temperatures. How could you use this data to obtain the enthalpy and entropy change associated with the reaction?

Simplest way would be to draw a graph of lnK against 1/T. The slope will be -Ho/R and the intercept will be So/R d) Look carefully at the vant Hoff equation. If the enthalpy change of the reaction is positive, will the equilibrium constant increase or decrease as the temperature is raised? What about if the enthalpy change is negative? You may find the alternative version of the equation given below easier to use for this K 2 H o T2 T1 ln = K1 R T1T2 If the enthalpy change is positive, the right hand side of the above equation will also be positive and therefore K2>K1. The opposite applies for an exothermic reaction. e) In the light of your answer to (d), if the complexation reaction is endothermic and the temperature is increased, will the reaction result in a greater or lesser formation of the complex? What if the reaction is exothermic?

If a reaction is endothermic, increasing the temperature will drive that reaction forward (i.e. the equilibrium will shift in the direction of the products). If it is exothermic, then the reaction will not proceed to such a great extent as the temperature is increased (i.e. the equilibrium will shift in the direction of the reactants).

2) Answer the following multiple choice questions: i) Which ONE of the following statements is TRUE? a) The total volume is the sum of the partial molar volumes b) The partial molar volume is a fixed value for any given substance c) The total volume is the sum of the partial molar volumes multiplied by the quantities added d) For a real solution the total volume will be the sum of the volumes of the two liquids added a) is FALSE because the total volume is the sum of the partial molar volumes multiplied by their quantities b) is FALSE because the partial molar volume is dependent on the composition of the final solution (see ethanol and water diagrams) c) is TRUE cf V = n1V1 + n2V2 d) is FALSE because for real solutions the total volume is different to sum of individual components due to interactions (cf Raoults law) ii): Which ONE of the following statements is FALSE. a) The chemical potential gives you information on the free energy contribution of individual components in a solution b) A system will tend to go from a high chemical potential to a low one c) When the chemical potentials of the products and reactants are the same there is a net conversion of products to reactants in the system. d) The chemical potential of a given substance is the free energy change per unit amount of that substance added to a solution a) is TRUE chemical potentials tell you how much the free energy rises on adding that material b) is TRUE chemical potential drives the reaction so it will take place so as to lose free energy (-ve free energy change) c) is FALSE when the chemical potentials are the same the reaction will be in equilibrium d) is TRUE this is a definition of chemical potential iii) Which ONE of the following statements is FALSE? a) When a system is at equilibrium the free energy change for the reaction is zero b) The equilibrium constant for the reaction of a chemical substance R to form the chemical substance S is the concentration of R divided by the concentration of S c) At dynamic equilibrium the forward and reverse reactions balance each other d) A very high value of the equilibrium constant K generally means that the reaction proceeds to near completion a) is TRUE equilibrium is where there is no free energy difference between reactants and products to drive the reaction in one direction or other b) is FALSE it is the other way round ([S] divided by [R]) c) is TRUE at dynamic equilibrium both reactions occur at equivalent rates

d) is TRUE a high K implies that the concentration of reactants is much lower than that of products when the reaction has reached equilibrium. 3) You are preparing solutions of a drug with a molecular weight of 245g/mole. a) You add 2.5g of drug to 40 mls of water. How many moles of drug are present in 2.5g? No of moles = mass/molecular weight = 2.5/245 = 1.02x10-2 b) What is the mole fraction of drug present in solution? No of moles of water in 40 mls (40g) = 40/18 = 2.22 Total number of moles present = 2.23 (moles of water and moles of drug) Mole fraction of drug = 0.01/2.23 = 0.0045 c) Is it possible to state the % w/v of this solution? Explain your answer No because we do not know the total volume of the solution once drug is dissolved d) You now have another solution containing 10mg/ml of the same drug in pH 8.0 buffer. What is the molarity of this solution? 10mg in 1ml = 10g in 1L 10g drug = 10/245 moles = 0.041moles 0.041moles in 1L = 0.041M solution e) You take 0.5mls of this solution and make up to 10mls using the same buffer. What is the new concentration in mg/ml, % w/v and molarity? 0.5mls of 10mg/ml solution contains 5mg of drug. This is now in 10mls, so new concentration is 5mg/10mls or 50mg in 100mls, 500mg in 1L or 0.5mg in 1ml Concentrations are 0.5mg/ml, 0.05% w/v and (0.5g/245 =) 0.002moles/L (2mM) There are quick ways of calculating dilutions but long hand is safer!