ATKINS' PHYSICAL CHEMISTRY
ATKINS' PHYSICAL CHEMISTRY
11th Edition
ISBN: 9780190053956
Author: ATKINS
Publisher: Oxford University Press
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Chapter 7, Problem 7A.10P

(a)

Interpretation Introduction

Interpretation:

The dimensions of θE is of temperature has to be confirmed.  The criterion for the validity of the high-temperature form of Einstein equation in terms of θE has to be stated.  The value of θE has to be calculated for diamond.

Concept introduction:

The Einstein temperature is denoted by θE.  It is characteristic to solids.  The value of heat capacities at low temperature, using the Einstein’s introduction of quantization is calculated by the following formula.

    CV,m(T)=3R[(θET)2eθE/T]

(a)

Expert Solution
Check Mark

Answer to Problem 7A.10P

The dimensions of θE is of temperature is validated.  The criterion for the validity of the high-temperature form of Einstein equation in terms of θE is T>>θE.  The value of θE for diamond is 2231.8K_.

Explanation of Solution

The value of Einstein temperature (θE) is expressed as,

    θE=hvk                                                                                                         (1)

Where,

  • h is the Planck’s constant.
  • v is the frequency.
  • k is the Boltzmann’s constant.

The units of h is Js.

The units of v is s1.

The units of k is JK1.

Substitute the units of h, v and k in equation (1).

    θE=Js×s1JK1=K

Hence, the dimensions are of the temperature.

For the calculation of heat capacity Einstein gave a quantitative explanation, which is shown by the formula below.

    CV,m(T)=3R[(θET)2(eθE/2TeθE/T1)2]                                                               (2)

Where,

  • CV,m(T) is the heat capacity at temperature T.
  • R is the gas constant.
  • θE is the Einstein’s temperature.

Assume,

  θE2T=x and θET=y

Substitute the values of x and y in equation (2).

    CV,m(T)=3R[(θET)2(exey1)2]                                                                   (3)

Expand ex and ey as shown below.

    ex=1+x+12x2+...ey=1+y+12y2+...

Substitute the values of ex and ey in equation (3).

    CV,m(T)=3R[(θET)2(1+x(1+y)1)2]

Now, substitute the values of x and y in the above equation.

    CV,m(T)=3R[(θET)2(1+θE2T(1+θET)1)2]

At high temperature, T>>θE.  Therefore,

    (θET)2(1+θE2T(1+θET)1)1

Hence, the heat capacity becomes,

    CV,m(T)=3R×1=3R

The classical value of heat capacity is 3R.  Therefore, the Einstein equation behaves classically at high temperatures.

Hence, the criterion for the validity of the high-temperature form of Einstein equation in terms of θE is T>>θE.

The value of v is 46.5THz.

The conversion of THz to s1 is done as,

    v=46.5THz(1012Hz1THz)(1s11Hz)=46.5×1012s1

The value of h is 6.626×1034kgm2/s.

The value of k is 1.38×1023kgm2s2.

The value of v is 46.5×1012s1.

Substitute the value of v, h k and in equation (1).

    θE=6.626×1034Js×46.5×1012s11.38×1023JK1=3.08×10201.38×1023=2231.8K_

Hence, the value of θE for diamond is 2231.8K_.

(b)

Interpretation Introduction

Interpretation:

The dimensions of θE is of temperature has to be confirmed.  The criterion for the validity of the high-temperature form of Einstein equation in terms of θE has to be stated.  The value of θE has to be calculated for copper.

Concept introduction:

The Einstein temperature is denoted by θE.  It is characteristic to solids.  The value of heat capacities at low temperature, using the Einstein’s introduction of quantization is calculated by the following formula.

    CV,m(T)=3R[(θET)2eθE/T]

(b)

Expert Solution
Check Mark

Answer to Problem 7A.10P

The dimensions of θE is of temperature is validated.  The criterion for the validity of the high-temperature form of Einstein equation in terms of θE is T>>θE.  The value of θE for copper is 343.3K_.

Explanation of Solution

The value of θE is,

    θE=hvk                                                                                                         (1)

Where,

  • h is the Planck’s constant.
  • v is the frequency.
  • k is the Boltzmann’s constant.

The units of h is Js.

The units of v is s1.

The units of k is JK1.

Substitute the units of h, v and k in equation (2).

    θE=Js×s1JK1=K

Hence, the dimensions are of the temperature.

For the calculation of heat capacity Einstein gave a quantitative explanation, which is shown by the formula below.

    CV,m(T)=3R[(θET)2(eθE/2TeθE/T1)2]                                                               (2)

Where,

  • CV,m(T) is the heat capacity at temperature T.
  • R is the gas constant.
  • θE is the Einstein’s temperature.

Assume,

  x=θE2T and y=θET

Substitute the value of x and y in equation (1).

    CV,m(T)=3R[(θET)2(exey1)2]                                                                   (3)

Expand ex and ey as shown below.

    ex=1+x+12x2+...ey=1+y+12y2+...

Substitute the values of ex and ey in equation (3).

    CV,m(T)=3R[(θET)2(1+x(1+y)1)2]

Now, substitute the values of x and y in the above equation.

    CV,m(T)=3R[(θET)2(1+θE2T(1+θET)1)2]

At high temperature, T>>θE.  Therefore,

    (θET)2(1+θE2T(1+θET)1)1

Hence, the heat capacity becomes,

    CV,m(T)=3R×1=3R

The classical value of heat capacity is 3R.  Therefore, the Einstein equation behaves classically at high temperatures.

Hence, the criterion for the validity of the high-temperature form of Einstein equation in terms of θE is T>>θE.

The value of v is 7.15THz.

The conversion of THz to s1 is done as,

    v=7.15THz(1012Hz1THz)(1s11Hz)=7.15×1012s1

The value of v is 7.15×1012s1.

The value of h is 6.626×1034kgm2/s.

The value of k is 1.38×1023kgm2s2.

Substitute the value of v, h k and in equation (1).

    θE=6.626×1034Js×7.15×1012s11.38×1023JK1=4.73×10211.38×1023=343.3K_

Hence, the value of θE for copper is 343.3K_.

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Chapter 7 Solutions

ATKINS' PHYSICAL CHEMISTRY

Ch. 7 - Prob. 7D.1STCh. 7 - Prob. 7E.1STCh. 7 - Prob. 7E.2STCh. 7 - Prob. 7F.1STCh. 7 - Prob. 7A.1DQCh. 7 - Prob. 7A.2DQCh. 7 - Prob. 7A.3DQCh. 7 - Prob. 7A.4DQCh. 7 - Prob. 7A.1AECh. 7 - Prob. 7A.1BECh. 7 - Prob. 7A.2AECh. 7 - Prob. 7A.2BECh. 7 - Prob. 7A.3AECh. 7 - Prob. 7A.3BECh. 7 - Prob. 7A.4AECh. 7 - Prob. 7A.4BECh. 7 - Prob. 7A.5AECh. 7 - Prob. 7A.5BECh. 7 - Prob. 7A.6AECh. 7 - Prob. 7A.6BECh. 7 - Prob. 7A.7AECh. 7 - Prob. 7A.7BECh. 7 - Prob. 7A.8AECh. 7 - Prob. 7A.8BECh. 7 - Prob. 7A.9AECh. 7 - Prob. 7A.9BECh. 7 - Prob. 7A.10AECh. 7 - Prob. 7A.10BECh. 7 - Prob. 7A.11AECh. 7 - Prob. 7A.11BECh. 7 - Prob. 7A.12AECh. 7 - Prob. 7A.12BECh. 7 - Prob. 7A.13AECh. 7 - Prob. 7A.13BECh. 7 - Prob. 7A.1PCh. 7 - Prob. 7A.2PCh. 7 - Prob. 7A.3PCh. 7 - Prob. 7A.4PCh. 7 - Prob. 7A.5PCh. 7 - Prob. 7A.6PCh. 7 - Prob. 7A.7PCh. 7 - Prob. 7A.8PCh. 7 - Prob. 7A.9PCh. 7 - Prob. 7A.10PCh. 7 - Prob. 7B.1DQCh. 7 - Prob. 7B.2DQCh. 7 - Prob. 7B.3DQCh. 7 - Prob. 7B.1AECh. 7 - Prob. 7B.1BECh. 7 - Prob. 7B.2AECh. 7 - Prob. 7B.2BECh. 7 - Prob. 7B.3AECh. 7 - Prob. 7B.3BECh. 7 - Prob. 7B.4AECh. 7 - Prob. 7B.4BECh. 7 - Prob. 7B.5AECh. 7 - Prob. 7B.5BECh. 7 - Prob. 7B.6AECh. 7 - Prob. 7B.6BECh. 7 - Prob. 7B.7AECh. 7 - Prob. 7B.7BECh. 7 - Prob. 7B.8AECh. 7 - Prob. 7B.8BECh. 7 - Prob. 7B.1PCh. 7 - Prob. 7B.2PCh. 7 - Prob. 7B.3PCh. 7 - Prob. 7B.4PCh. 7 - Prob. 7B.5PCh. 7 - Prob. 7B.7PCh. 7 - Prob. 7B.8PCh. 7 - Prob. 7B.9PCh. 7 - Prob. 7B.11PCh. 7 - Prob. 7C.1DQCh. 7 - Prob. 7C.2DQCh. 7 - Prob. 7C.3DQCh. 7 - Prob. 7C.1AECh. 7 - Prob. 7C.1BECh. 7 - Prob. 7C.2AECh. 7 - Prob. 7C.2BECh. 7 - Prob. 7C.3AECh. 7 - Prob. 7C.3BECh. 7 - Prob. 7C.4AECh. 7 - Prob. 7C.4BECh. 7 - Prob. 7C.5AECh. 7 - Prob. 7C.5BECh. 7 - Prob. 7C.6AECh. 7 - Prob. 7C.6BECh. 7 - Prob. 7C.7AECh. 7 - Prob. 7C.7BECh. 7 - Prob. 7C.8AECh. 7 - Prob. 7C.8BECh. 7 - Prob. 7C.9AECh. 7 - Prob. 7C.9BECh. 7 - Prob. 7C.10AECh. 7 - Prob. 7C.10BECh. 7 - Prob. 7C.1PCh. 7 - Prob. 7C.2PCh. 7 - Prob. 7C.3PCh. 7 - Prob. 7C.4PCh. 7 - Prob. 7C.5PCh. 7 - Prob. 7C.6PCh. 7 - Prob. 7C.7PCh. 7 - Prob. 7C.8PCh. 7 - Prob. 7C.9PCh. 7 - Prob. 7C.11PCh. 7 - Prob. 7C.12PCh. 7 - Prob. 7C.13PCh. 7 - Prob. 7C.14PCh. 7 - Prob. 7C.15PCh. 7 - Prob. 7D.1DQCh. 7 - Prob. 7D.2DQCh. 7 - Prob. 7D.3DQCh. 7 - Prob. 7D.1AECh. 7 - Prob. 7D.1BECh. 7 - Prob. 7D.2AECh. 7 - Prob. 7D.2BECh. 7 - Prob. 7D.3AECh. 7 - Prob. 7D.3BECh. 7 - Prob. 7D.4AECh. 7 - Prob. 7D.4BECh. 7 - Prob. 7D.5AECh. 7 - Prob. 7D.5BECh. 7 - Prob. 7D.6AECh. 7 - Prob. 7D.6BECh. 7 - Prob. 7D.7AECh. 7 - Prob. 7D.7BECh. 7 - Prob. 7D.8AECh. 7 - Prob. 7D.8BECh. 7 - Prob. 7D.9AECh. 7 - Prob. 7D.9BECh. 7 - Prob. 7D.10AECh. 7 - Prob. 7D.10BECh. 7 - Prob. 7D.11AECh. 7 - Prob. 7D.11BECh. 7 - Prob. 7D.12AECh. 7 - Prob. 7D.12BECh. 7 - Prob. 7D.13AECh. 7 - Prob. 7D.13BECh. 7 - Prob. 7D.14AECh. 7 - Prob. 7D.14BECh. 7 - Prob. 7D.15AECh. 7 - Prob. 7D.15BECh. 7 - Prob. 7D.1PCh. 7 - Prob. 7D.2PCh. 7 - Prob. 7D.3PCh. 7 - Prob. 7D.4PCh. 7 - Prob. 7D.5PCh. 7 - Prob. 7D.6PCh. 7 - Prob. 7D.7PCh. 7 - Prob. 7D.8PCh. 7 - Prob. 7D.9PCh. 7 - Prob. 7D.11PCh. 7 - Prob. 7D.12PCh. 7 - Prob. 7D.14PCh. 7 - Prob. 7E.1DQCh. 7 - Prob. 7E.2DQCh. 7 - Prob. 7E.3DQCh. 7 - Prob. 7E.1AECh. 7 - Prob. 7E.1BECh. 7 - Prob. 7E.2AECh. 7 - Prob. 7E.2BECh. 7 - Prob. 7E.3AECh. 7 - Prob. 7E.3BECh. 7 - Prob. 7E.4AECh. 7 - Prob. 7E.4BECh. 7 - Prob. 7E.5AECh. 7 - Prob. 7E.5BECh. 7 - Prob. 7E.6AECh. 7 - Prob. 7E.6BECh. 7 - Prob. 7E.7AECh. 7 - Prob. 7E.7BECh. 7 - Prob. 7E.8AECh. 7 - Prob. 7E.8BECh. 7 - Prob. 7E.9AECh. 7 - Prob. 7E.9BECh. 7 - Prob. 7E.1PCh. 7 - Prob. 7E.2PCh. 7 - Prob. 7E.3PCh. 7 - Prob. 7E.4PCh. 7 - Prob. 7E.5PCh. 7 - Prob. 7E.6PCh. 7 - Prob. 7E.7PCh. 7 - Prob. 7E.8PCh. 7 - Prob. 7E.9PCh. 7 - Prob. 7E.12PCh. 7 - Prob. 7E.15PCh. 7 - Prob. 7E.16PCh. 7 - Prob. 7E.17PCh. 7 - Prob. 7F.1DQCh. 7 - Prob. 7F.2DQCh. 7 - Prob. 7F.3DQCh. 7 - Prob. 7F.1AECh. 7 - Prob. 7F.1BECh. 7 - Prob. 7F.2AECh. 7 - Prob. 7F.2BECh. 7 - Prob. 7F.3AECh. 7 - Prob. 7F.3BECh. 7 - Prob. 7F.4AECh. 7 - Prob. 7F.4BECh. 7 - Prob. 7F.5AECh. 7 - Prob. 7F.5BECh. 7 - Prob. 7F.6AECh. 7 - Prob. 7F.6BECh. 7 - Prob. 7F.7AECh. 7 - Prob. 7F.7BECh. 7 - Prob. 7F.8AECh. 7 - Prob. 7F.8BECh. 7 - Prob. 7F.9AECh. 7 - Prob. 7F.9BECh. 7 - Prob. 7F.10AECh. 7 - Prob. 7F.10BECh. 7 - Prob. 7F.11AECh. 7 - Prob. 7F.11BECh. 7 - Prob. 7F.12AECh. 7 - Prob. 7F.12BECh. 7 - Prob. 7F.13AECh. 7 - Prob. 7F.13BECh. 7 - Prob. 7F.14AECh. 7 - Prob. 7F.14BECh. 7 - Prob. 7F.1PCh. 7 - Prob. 7F.4PCh. 7 - Prob. 7F.6PCh. 7 - Prob. 7F.7PCh. 7 - Prob. 7F.8PCh. 7 - Prob. 7F.9PCh. 7 - Prob. 7F.10PCh. 7 - Prob. 7F.11PCh. 7 - Prob. 7.3IACh. 7 - Prob. 7.4IACh. 7 - Prob. 7.5IACh. 7 - Prob. 7.6IA
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