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At certain states, the \(p-v-T\) data of a gas can be expressed as \(Z=1-A p / T^{4}\), where \(Z\) is the compressibility factor and \(A\) is a constant. (a) Obtain an expression for \((\partial p / \partial T)_{v}\) in terms of \(p, T, A\), and the gas constant \(R\). (b) Obtain an expression for the change in specific entropy, \(\left[s\left(p_{2}, T\right)-s\left(p_{1}, T\right)\right]\) (c) Obtain an expression for the change in specific enthalpy, \(\left[h\left(p_{2}, T\right)-h\left(p_{1}, T\right)\right]\)

Short Answer

Expert verified
\( \left( \frac{\partial p}{\partial T} \right)_{v} = R \left( \frac{1}{V + \frac{AV}{T^{3}}} - \frac{AV}{T^{4}} \right) \);\left[ s(p_{2},T) - s(p_{1},T) = -R \ln \left( \frac{p_{2}}{p_{1}} \right) + \frac{AR}{T^{4}}(p_{2}-p_{1}) \]; h(p_{2},T) - h(p_{1},T) = RT\left( -\ln\left( \frac{p_{2}}{p_{1}} \right) + \frac{A}{T^{4}} \right)(p_{2} - p_{1})\.

Step by step solution

01

Understanding the given equation

The compressibility factor is given by the equation: \[Z=1-\frac{A p}{T^{4}}\]where \(Z\) is the compressibility factor, \(A\) is a constant, \(p\) is pressure, and \(T\) is temperature.
02

Obtain expression for \((\partial p / \partial T)_{v}\)

At constant volume \(v\), the compressibility factor is related to the pressure and temperature. We need to use the equation:\[Z = \frac{pV}{RT}\]where \(V\) is the volume and \(R\) is the gas constant. Now, substitute the given expression for \(Z\):\[1-\frac{A p}{T^{4}} = \frac{pV}{RT}\]Let's rearrange to isolate \(p\):\[pV = RT - \frac{ARp}{T^{3}}V\]\[pV \left(1 + \frac{AV}{T^{3}}\right) = RT\]Finally, solving for \(p\) we get:\[p = \frac{RT}{V + \frac{AV}{T^{3}}}\] Now, differentiate \(p\) with respect to \(T\):\[ \left( \frac{\partial p}{\partial T} \right)_{v} = R \left( \frac{1}{V + \frac{AV}{T^{3}}} - \frac{AV}{T^{4}} \right) \]
03

Obtain expression for entropy change \(\left[s\left(p_{2}, T\right)-s\left(p_{1}, T\right)\right]\)

Using the Maxwell relations, we know that:\[ \left( \frac{\partial s}{\partial p} \right)_{T} = -\left( \frac{\partial v}{\partial T} \right)_{p}\]Substituting the volume from the given equation, we get:\[ \left( \frac{\partial v}{\partial T} \right)_{p} = \frac{R}{p} - \frac{AR}{T^{4}p}\]Integrate with respect to \(p\) from \(p_{1}\) to \(p_{2}\):\[ s(p_{2},T) - s(p_{1},T) = - \int_{p_{1}}^{p_{2}} \left( \frac{R}{p} - \frac{AR}{T^{4}p} \right) dp = -R \ln\left( \frac{p_{2}}{p_{1}} \right) + \frac{AR}{T^{4}}(p_{2}-p_{1}) \]
04

Obtain expression for enthalpy change \(\left[h\left(p_{2}, T\right)-h\left(p_{1}, T\right)\right]\)

Using the relationship for enthalpy change:\[ dh = T ds + v dp \]From the equation:\[ v = \frac{RT}{p}(1 - \frac{A}{T^{4}} p) \]Substitute this in the enthalpy change equation and integrate between \(p_{1}\) and \(p_{2}\):\[ h(p_{2},T) - h(p_{1},T) = T \left[-R \ln \left( \frac{p_{2}}{p_{1}} \right) + \frac{AR}{T^{4}} (p_{2} - p_{1}) \right] + \int_{p_{1}}^{p_{2}} \frac{RT}{p}(1 - \frac{A}{T^{4}}p)dp \]Solving this we get:\[ h(p_{2},T) - h(p_{1},T) = RT\left( -\ln\left( \frac{p_{2}}{p_{1}} \right) + \frac{A}{T^{4}} \right)(p_{2} - p_{1}) \]

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Partial Derivative of Pressure with Respect to Temperature
In thermodynamics, understanding the relation between pressure (p) and temperature (T) at constant volume (v) is crucial. This is captured by the partial derivative \(\frac{\text{∂} p}{\text{∂} T} \) at constant volume. For a given gas, we know the compressibility factor (Z) is expressed as \[Z = 1 - \frac{A p}{T^4}\text{,}\] where A is a constant. We also use the ideal gas law \[Z = \frac{pV}{RT}\] to relate pressure, volume (V), and the gas constant (R). By substituting the expression for Z and rearranging, we obtain a formula for pressure in terms of T, V, R, and A. From here, we differentiate with respect to T to find the partial derivative of p with respect to T at constant volume. The result helps us understand how pressure changes with temperature under constant volume conditions.
Specific Entropy Change
Entropy (s) is a measure of disorder or randomness in a system. The change in specific entropy when moving between two states at different pressures but constant temperature can be calculated using Maxwell relations. Given \[ \frac{\text{∂} s}{\text{∂} p} = -\frac{\text{∂} v}{\text{∂} T} \] and substituting volume (v) from the given compressibility factor equation, we integrate this expression to find the entropy difference. The result includes two key components: a term involving the natural logarithm of the pressure ratio, and another involving the constant A and temperature. These contributions help us understand how pressure changes influence entropy.
Specific Enthalpy Change
Enthalpy (h) reflects the total heat content of a system. When calculating the specific enthalpy change between two states, we use the relationship: \[ \text{d}h = T \text{d}s + v \text{d}p \] By substituting the expression for volume in terms of temperature, pressure, and the constant A, we integrate to obtain the total change in enthalpy. This provides insight into how thermal energy and work contributions drive changes in system states. The resulting equation comprises terms for both entropic and volumetric contributions, illustrating the complex interplay between energy, pressure, and temperature.
Maxwell Relations
Maxwell relations are a set of equations derived from the fundamental thermodynamic potentials. These relations provide connections between different partial derivatives of thermodynamic quantities. For instance, one of the Maxwell relations tells us: \[ \frac{\text{∂} s}{\text{∂} p} = -\frac{\text{∂} v}{\text{∂} T} \] This relation links entropy (s) to volume (v) and pressure (p) to temperature (T), enabling us to derive expressions for changes in entropy or enthalpy. These relations help simplify calculations in thermodynamics by providing shortcuts to otherwise complex derivations.
Ideal Gas Law
The ideal gas law is a fundamental principle in thermodynamics expressed as: \[ pV = nRT \] where p is pressure, V is volume, n is the number of moles, R is the gas constant, and T is temperature. This law assumes that gases consist of many small particles moving randomly. It provides a simple relationship between pressure, volume, and temperature for ideal gases. Although real gases deviates from this behavior, especially at high pressure and low temperature, the ideal gas law is an essential approximation for understanding gas properties and behaviors under standard conditions.

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Most popular questions from this chapter

The volume of a \(1-\mathrm{kg}\) copper sphere is not allowed to vary by more than \(0.1 \%\). If the pressure exerted on the sphere is increased from 10 bar while the temperature remains constant at \(300 \mathrm{~K}\), determine the maximum allowed pressure, in bar. Average values of \(\rho, \beta\), and \(\kappa\) are \(8888 \mathrm{~kg} / \mathrm{m}^{3}, 49.2 \times 10^{-6}\) \((\mathrm{K})^{-1}\), and \(0.776 \times 10^{-11} \mathrm{~m}^{2} / \mathrm{N}\), respectively.

For a gas whose \(p-v-T\) behavior is described by \(Z=1+\) \(B p / R T\), where \(B\) is a function of temperature, derive expressions for the specific enthalpy, internal energy, and entropy changes, \(\left[h\left(p_{2}, T\right)-h\left(p_{1}, T\right)\right],\left[u\left(p_{2}, T\right)-u\left(p_{1}, T\right)\right]\), and \(\left[s\left(p_{2}, T\right)-s\left(p_{1}, T\right)\right]\)

Complete the following exercises dealing with slopes: (a) At the triple point of water, evaluate the ratio of the slope of the vaporization line to the slope of the sublimation line. Use steam table data to obtain a numerical value for the ratio. (b) Consider the superheated vapor region of a temperature-entropy diagram. Show that the slope of a constant specific volume line is greater than the slope of a constant pressure line through the same state. (c) An enthalpy-entropy diagram (Mollier diagram) is often used in analyzing steam turbines. Obtain an expression for the slope of a constant-pressure line on such a diagram in terms of \(p-v-T\) data only. (d) A pressure-enthalpy diagram is often used in the refrigeration industry. Obtain an expression for the slope of an isentropic line on such a diagram in terms of \(p-v-T\) data only.

Propane \(\left(\mathrm{C}_{3} \mathrm{H}_{8}\right.\) ) enters a turbine operating at steady state at 100 bar, \(400 \mathrm{~K}\) and expands isothermally without irreversibilities to 10 bar. There are no significant changes in kinetic or potential energy. Using data from the generalized fugacity chart, determine the power developed, in \(\mathrm{kW}\), for a mass flow rate of \(50 \mathrm{~kg} / \mathrm{min}\).

Nitrogen \(\left(\mathrm{N}_{2}\right)\) enters a compressor operating at steady state at \(1.5 \mathrm{MPa}, 300 \mathrm{~K}\) and exits at \(8 \mathrm{MPa}, 500 \mathrm{~K}\). If the work input is \(240 \mathrm{~kJ}\) per \(\mathrm{kg}\) of nitrogen flowing, determine the heat transfer, in kJ per \(\mathrm{kg}\) of nitrogen flowing. Ignore kinetic and potential energy effects.

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