[試題] 101下 物理化學 戴子安 期末考
課程名稱︰物理化學2
課程性質︰必帶
課程教師︰戴梓安
開課學院：工學院
開課系所︰化工系
考試日期（年月日）︰2013/6/17
考試時限（分鐘）：120分鐘
是否需發放獎勵金：是
（如未明確表示，則不予發放）
試題 :
1.(20 points) Explain the following terms. Use graph if necessary.
(a) The Einstein-Stokes' law.
(b)Fick's second law for 3 dimensional diffusion.
(c) The material balance equation for a 1st order reaction.
(d)Oswald's dilution law.
(e) Nernst=einstein equation. + _
(f)If a reaction can be catalyzed by H and OH , plot the different variations
of log k v.s. pH.
10
(g) For an enzyme reaction, plot 1/v v.s. 1/[S] for competitive,
0
un competitive, and noncompetitive inhibition reactions.
(h) TheLotka Model.
(i)What is < n > for polymer chains synthesized in the step-growth
polymerization for monomer conversion P=0.999?
2.(10points) The mutarotation of glucose is first order in glucose
concentration and is catalyzed by acids (A) and base(B). the first-order
rate constant may be expressed by an equation of the type that is
encountered in reaction with parallel paths.
+
k = k + k [H ] + k [A] + k [B]
0 H+ A B
. -1
The following data is obtained at 18 C in a medium containing 0.02 mol L
sodium acetate and various concentartions of acetic acid.
┌─────────┬───────┬────────┬──────┐
│ -1 │ │ │ │
│CH COOH/mol L │ 0.02 │ 0.105 │ 0.199 │
│ 3 │ │ │ │
├─────────┼───────┼────────┼──────┤
│ -4 -1 │ │ │ │
│ k/10 min │ 1.36 │ 1.40 │ 1.46 │
└─────────┴───────┴────────┴──────┘
Calculate k and k , The term involving k is negligible under these
0 A H+
conditions.
-1
3.(10points) the molecular weight of bovine serum albumin (BSA) is 66500gmol
3 -1
and has a specific volume of 0.717 cm g . Velocity centrufugation
_ -13
demonstrates that s = 4.31 x 10 s for this protein. Assuming a
-3
solution density of 1.0 g cm and viscosity of 1.0 cP , determine the
friction coefficient and effective radius of BSA.
-1 -1
(1 Poise = 0.1 kg m s )
4.(10points) The following molar conductivity data are obtained for an
electrolyte:
┌────────────────┬─────────────────┐
│ │ 2 -1 │
│ concentration (M) │ Am (Sm mol ) │
│ │ │
├────────────────┼─────────────────┤
│0.0005 │ 0.01245 │
├────────────────┼─────────────────┤
│0.001 │ 0.01237 │
├────────────────┼─────────────────┤
│0.005 │ 0.01207 │
├────────────────┼─────────────────┤
│0.01 │ 0.01185 │
├────────────────┼─────────────────┤
│ 0.02 │ 0.01158 │
├────────────────┼─────────────────┤
│0.05 │ 0.01111 │
├────────────────┼─────────────────┤
│0.1 │ 0.01067 │
└────────────────┴─────────────────┘
.
Determine if the electrolyte is strong or weak, and Λ .
m
5.(10 points) The rate of reaction can be determined by measuring the change
in potical rotation of the sample as a function of time if a reactant or
product is chiral. This technique is especailly useful for kinetic studies
of enzyme catalysis involving sugars. For example, The enzyme invertase
catalyzes the hydrolysis of sucrose, an optically active sugar. The initial
reaction rates as a function of sucrose concentration are as follows:
┌────────────────┬─────────────────┐
│ │ -1 │
│ [sucrose] (M) │ rate(M s ) │
│ 0 │ │
├────────────────┼─────────────────┤
│0.029 │ 0.182 │
├────────────────┼─────────────────┤
│0.059 │ 0.266 │
├────────────────┼─────────────────┤
│0.088 │ 0.31 │
├────────────────┼─────────────────┤
│0.117 │ 0.33 │
├────────────────┼─────────────────┤
│ 0.175 │ 0.372 │
├────────────────┼─────────────────┤
│0.234 │ 0.371 │
└────────────────┴─────────────────┘
Use these data to determine the Micahaelis constant for invertase.
6.(10 points) Derive the rate constant for a reaction in which the two
reaction in which the two reactant neutral molecules(A and B) reacts if
they come within a distant r of one another by diffusion is
AB
k = 4π。 N 。 r 。 D .
-1 A AB AB
7.(10 points) Consider a chain polymerization process
(a) Initiation I → R。 + R。 v = k [I]；M + R →M 。 fast
i i 1
(b) Propagation M + M 。 → 。M ... M + M → 。M v = k [M][。M]
1 2 n-1 n p p
2
(c) termination (mutual termination) 。M + 。M → M v = k [。M]
n m n+m t t
Calculate the average polymer length in a polymer produced by the mechanism.
8.(10points) Use the following data to determine the Langmuir adsorption
parameters for nitrogen on mica:
┌────────────────┬─────────────────┐
│ │ 2 -1 │
│ P(torr) │ V (cm g ) │
│ │ ads │
├────────────────┼─────────────────┤
│ -3 │ │
│ 2.1 x 10 │ 0.494 │
├────────────────┼─────────────────┤
│ -3 │ │
│ 4.6 x 10 │ 0.782 │
├────────────────┼─────────────────┤
│ -3 │ │
│ 1.3 x 10 │ 1.16 │
│ │ │
└────────────────┴─────────────────┘
9.(10 points) The data below relates to the adsorption of N on rutile(TiO )
2 2
at 75K. Confirm that they fit a BET isotherm in the range of pressures
reported, and determine V and c.
m
┌───────┬───┬───┬───┬───┬───┬───┬────┐
│ P/kPa │ 0.16 │1.87 │ 6.11 │ 11.67│ 17.02│ 21.92│ 27.29 │
├───────┼───┼───┼───┼───┼───┼───┼────┤
│ 3 │ │ │ │ │ │ │ │
│V/mm │ 601 │ 720 │ 822 │ 935 │ 1046 │ 1146 │ 1254 │
└───────┴───┴───┴───┴───┴───┴───┴────┘
At 75K , P* = 76 kPa. The volumes have been corrected to 1atm and 273K and
referred to 1.00g of substrate.
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