Water anomaly -- Heat capacities

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The discussion centers on the relationship between specific heat capacities at constant pressure (C_p) and constant volume (C_v), particularly for water. It is established that for water, the derivative (∂V/∂T)_P is negative, leading to the conclusion that C_p is less than C_v. The reasoning highlights that at constant pressure, work is done to increase both temperature and volume, while at constant volume, no work is done for volume increase, resulting in C_p being greater than C_v for gases. Mayer's relation is referenced, indicating that for ideal gases, C_p is always greater than C_v, which extends to general substances like water due to positive thermal expansion and compressibility coefficients. Overall, the discussion confirms that C_p is generally greater than or equal to C_v across various 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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