Water anomaly -- Heat capacities

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SUMMARY

The forum discussion centers on the relationship between heat capacities of water, specifically the inequality \(C_p < C_v\) under certain conditions. The derived relation \(C_p - C_v = [P + (\frac{\partial U}{\partial V})_T](\frac{\partial V}{\partial T})_P\) indicates that for water, where \((\frac{\partial V}{\partial T})_P < 0\), the specific heat at constant pressure \(C_p\) is less than the specific heat at constant volume \(C_v\). This contrasts with ideal gases where \(C_p > C_v\) due to additional work done at constant pressure. The discussion also references Mayer's Relation and its applicability to homogeneous substances like water.

PREREQUISITES
  • Understanding of thermodynamic principles, specifically heat capacities
  • Familiarity with Mayer's Relation for ideal gases
  • Knowledge of isothermal compressibility and thermal expansion coefficients
  • Basic calculus for interpreting partial derivatives in thermodynamic equations
NEXT STEPS
  • Research the implications of Mayer's Relation on various substances beyond ideal gases
  • Study the thermal expansion coefficient and its effects on heat capacity
  • Explore the concept of isothermal compressibility in different phases of matter
  • Investigate the practical applications of heat capacities in engineering and physical sciences
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This discussion is beneficial for thermodynamics students, researchers in physical chemistry, and engineers working with thermal systems, particularly those focusing on the properties of water and other homogeneous substances.

LagrangeEuler
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From relation
C_p-C_v=[P+(\frac{\partial U}{\partial V})_T](\frac{\partial V}{\partial T})_P
In case of water ##(\frac{\partial V}{\partial T})_P<0## so ##C_p<C_v##? Right?
 
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LagrangeEuler said:
From relation
C_p-C_v=[P+(\frac{\partial U}{\partial V})_T](\frac{\partial V}{\partial T})_P
In case of water ##(\frac{\partial V}{\partial T})_P<0## so ##C_p<C_v##? Right?
(∂V/∂T)P is the amount of work done.
If we consider this amount of work done, in Cp, i.e, at constant pressure heat is absorbed and work is done, not only to increase the temperature of the gas (or the Substance) but also to increase the volume of the gas (Which, isn't constant here) which includes increasing both potential energies of the molecules and doing work against outside pressure, if any.For Cv, the whole of the energy spent and work done in terms of increase in volume is absent as this is done at constant volume. thus less work in done here. Hence, for gases, Cp>Cv.
P.S:
Mayer's Relation
Mayer derived a relation between specific heat at constant pressure and the specific heat at constant volume for an ideal gas. The relation is:

fcb51fbe67811de0312ab9aa406e4a60.png
,

where CP,m is the specific heat at constant pressure, CV,m is the specific heat at constant volume and R is the gas constant.

For more general homogeneous substances( which can be water), not just ideal gases, the difference takes the form,

d4ee6d4542130160b201991e75cc0c43.png

(see relations between heat capacities), where
9d5c5761a7454b5c7eaacae523a5704f.png
is the heat capacity of a body at constant pressure,
22151977c6d6a3d9d14caed2a5afaef5.png
is the heat capacity at constant volume,
5206560a306a2e085a437fd258eb57ce.png
is the volume,
b9ece18c950afbfa6b0fdbfa4ff731d3.png
is the temperature,
071997f13634882f823041b057f90923.png
is the thermal expansion coefficient and
3aaeac3c3684ef427a25ed04dd8fe956.png
is the isothermal compressibility.

From this relation, several inferences can be made:

  • Since isothermal compressibility
    3aaeac3c3684ef427a25ed04dd8fe956.png
    is positive for all phases and the square of thermal expansion coefficient
    a0d0d432dab07f6f48d729d730b2a497.png
    is a positive quantity or zero, the specific heat at constant-pressure is always greater than or equal to specific heat at constant-volume.
08a5990da9348b7bd1cf38a9b93e7a81.png
d06d73293ea32235c90ac400799011b7.png
 
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