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Thermodynamics
State Functions
Enthalpy
Last updated: 09:11, 7 Nov 2015
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When a process occurs at constant pressure, the heat evolved (either released or absorbed) is equal to the
change in enthalpy. Enthalpy (H ) is the sum of the internal energy (U ) and the product of pressure and
volume (P V ) given by the equation:
H = U + PV
When a process occurs at constant pressure, the heat evolved (either released or absorbed) is equal to the
change in enthalpy. Enthalpy is a state function which depends entirely on the state functions T , P and U .
Enthalpy is usually expressed as the change in enthalpy (H ) for a process between initial and nal states:
H = U + P V
If temperature and pressure remain constant through the process and the work is limited to pressure-volume
work, then the enthalpy change is given by the equation:
H = U + P V
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Also at constant pressure the heat ow (q ) for the process is equal to the change in enthalpy de ned by the
equation:
H = q
Sign
in
By looking at whether q is exothermic or endothermic we can determine a relationship between H and q .
If the reaction absorbs heat it is endothermic meaning the reaction consumes heat from the surroundings so
q > 0 (positive). Therefore, at constant temperature and pressure, by the equation above, if q is positive then
H is also positive. And the same goes for if the reaction releases heat, then it is exothermic, meaning the
system gives off heat to its surroundings, so q < 0 (negative). If q is negative, then H will also be negative.
(1)
Enthalpy can also be expressed as a molar enthalpy, H ,by dividing the enthalpy or change in enthalpy by
the number of moles. Enthalpy is a state function. This implies that when a system changes from one state to
another, the change in enthalpy is independent of the path between two states of a system.
m
If there is no non-expansion work on the system and the pressure is still constant, then the change in
enthalpy will equal the heat consumed or released by the system (q).
H = q
(2)
This relationship can help to determine whether a reaction is endothermic or exothermic. At constant
pressure, an endothermic reaction is when heat is absorbed. This means that the system consumes heat from
the surroundings, so q is greater than zero. Therefore according to the second equation, the H will also be
greater than zero. On the other hand, an exothermic reaction at constant pressure is when heat is released.
This implies that the system gives off heat to the surroundings, so q is less than zero. Furthermore, H will
be less than zero.
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(3)
T
)
T
(4)
where the subscript P indicates the derivative is done under constant pressure.
Standard Enthalpy of Vaporization (H ) isthe energy that must be supplied as heat at constant pressure
per mole of molecules vaporized (liquid to gas).
o
vap
fus
sub
sub
= H
fus
+ Hvap
The enthalpy of condensation is the reverse of the enthalpy of vaporization and the enthalpy of freezing is the
reverse of the enthalpy of fusion. The enthalpy change of a reverse phase transition is the negative of the
enthalpy change of the forward phase transition. Also the enthalpy change of a complete process is the sum
of the enthalpy changes for each of the phase transitions incorporated in the process.
Outside Links
Canagaratna, Sebastian G. "A Visual Aid in Enthalpy Calculations " J. Chem. Educ. 2000 77 1178.
Kennedy Sr., Alvin P. "Determination of Enthalpy of Vaporization Using a Microwave Oven " J. Chem. Educ.
1997 74 1231.
Treptow, Richard S. "How Thermodynamic Data and Equilibrium Constants Changed When the StandardState Pressure Became 1 Bar " J. Chem. Educ. 1999 76 212.
Yi, L., Sheng-Lu, K., Song-Sheng, Qu. "Some Views in the Internal Energy and Enthalpy of Gases." J. Chem.
Educ. 1995: 72, 408.
References
http://chem.libretexts.org/Core/Physical_Chemistry/Thermodynamics/State_Functions/Enthalpy
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1. Atkins, Peter and de Paula, Julio; Physical Chemistry for the Life Sciences, United States, 2006.Katherine
Hurley
2. Petrucci, et al. General Chemistry Principles & Modern Applications. 9th ed. Upper Saddle River, NJ:
Pearson Prentice Hall, 2007
Problems
1. Calculate the enthalpy (H) for the process in which 45.0 grams of water is converted from liquid at 10
C to vapor at 25 C.
Solution
Part 1: Heating water from 10.0 to 25.0 C
kJ = 45.0g H20 x (4.184J/gH2O C) x (25.0 - 10.0) C x 1kJ/1000J = 2.82 kJ
Part 2: Vaporizing water at 25.0 C
kJ = 45.0 g H2O x 1 mol H2O/18.02 g H2O x 44.0 kJ/1 mol H2O = 110 kJ
Part 3: Total Enthalpy Change
H = 2.82 kJ + 110kJ
Contributors
Katherine Hurley (UCD), Jennifer Shamieh (UCD)
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Assorted De nitions
Recommended articles
Heat of Vaporization
Heat of Fusion
Heat of Reaction
Heat of Sublimation
Standard Enthalpy of Formation
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