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Hess' Law
Hess' Law is named after Russian Chemist and Doctor Germain Hess. Hess helped formulate the early principles of thermochemistry. His most famous paper, which was published in 1840, included his law on thermochemistry. The law went on to be called Hess' Law of Constant Heat summation (sometimes referred to as Hess' Law) and it states that regardless of the multiple stages or steps of a reaction, enthalpy change overall encompasses the sum of all changes.

1. 2. 3. 4. 5. 6. 7. 1. 8. 9.
10.

1. Introduction 2. Definitions 3. Why it works 4. Steps involved in solving enthalpy of combustion problems 5. Standard Enthalpy of Formation 6. Standard Gibb's Energy of Formation 7. Standard Entropy 7.1. Steps 8. Outside Links 9. References 10. Contributors

Introduction
Hess' law is due to enthalpy being a state function, which allows us to calculate the overall change in enthalpy by simply summing up the changes for each step of the way, until product is formed. All steps have to proceed at the same temperature and the equations for the individual steps must balance out. Hess' law doesn't just apply to Enthalpy, it can also be used to calculate: (1) Standard Gibb's Energy of Formation and (2) Standard Reaction Entropy.

Definitions

The enthalpy of a given chemical reaction is constant, regardless of the reaction happening in one step or many steps. If a chemical equation can be written as the sum of several other chemical equations, the enthalpy change of the first chemical equation equals the sum of the enthalpy changes of the other chemical equations.

Why it works
The enthalpy of a reaction does not depend on the elementary steps, but on the final state of the products and initial state of the reactants. Enthalpy is an extensive property and hence changes when the size of the sample changes. This means that the enthalpy of the reaction scales proportionally to the moles used in the reaction. For instance, in the following reaction, one can see that doubling the molar amounts simply doubles the enthalpy of the reaction. H2 (g) + 1/2O2 (g) H2O (g) 2H2 (g) + O2 (g) 2H2O (g) H = -572 kJ H = -1144kJ

The sign of the reaction enthalpy changes when a process is reversed. H2 (g) + 1/2O2 (g) H2O (g) H = -572 kJ

When switched: H2O (g) H2 (g) + 1/2O2 (g) H = +572 kJ

Since enthalpy is a state function, it is path independent. Therefor, it does not matter what reactions one uses to obtain the final reaction.

Steps involved in solving enthalpy of combustion problems

1. 2. 3. 4. 5. Balance the individual equations If necessary look up standard enthalpies Flip equations around if necessary to cancel out terms on opposite sides Changing the equation around requires a sign change of the H of that individual step Sum up the individual steps

Example
Calculate the standard enthalpy of combustion of the transition of C(s, graphite) C(s, diamond), given C(s, graphite) + O2 CO2 Ho = -393.5 kJ/mol CO2 C(s, diamond) + O2 Ho = + 395.41 kJ/mol First we see that both equations are balanced. The enthalpies were given and there is no need to flip an equation around because it is possible to cancel out a couple terms as is. What is left is canceling out the O 2 and the CO2 species, writing the overall reaction and then summing the two enthalpies together. C(s, graphite) + O2 CO2 CO2 C(s, diamond) + O2 Overall Equation becomes: C(s, graphite) C(s, diamond)

adding the enthalpies gives (-393.5 kJ/mol + 395.41 kJ/mol) = + 1.91 kJ/mol Since the Ho is positive, the reaction is endothermic.

Standard Enthalpy of Formation

The following equation is used to calculate the Standard Enthalpy of Formation:

rH=H(products)H(reactants)

If Ho is positive, the reaction is endothermic If Ho is negative, the reaction is exothermic

Standard Gibb's Energy of Formation

As mentioned above, the Standard Gibb's Free Energy of Formation is calculated using the principles of Hess's law. The following equation is used for those calculations:

fG= vfG(products) vfG(reactants)

Standard Entropy
The Standard Entropy of a reaction is calculated using the following equation:

rS=S(products)S(reactants) Example
Using Hess Law, the enthalpy of reaction of the major process of steam reforming can be determined. CH4(g) + H2O(l) CO(g) + 3H2(g) H = ??

Using the two postulates, given enough information, we are able to solve the enthalpy of reaction of an untabulated equation. Using the reaction of Carbon Dioxide and Hydrogen gas and reaction of methane decomposition; 1) CO(g) + H2(g) C(graphite) + H2O(g) 2) C(graphite) + 2H2(g) CH4(g) H = -131.3 kJ H = -74.8 kJ

Steps
1. 1. 2. 1. 3. Flip Equation #2 to and change the sign of the enthalpy reaction . Ex. CH4(g) C(graphite) + 2H2(g) H = +74.8 Flip Equation #1 as well in order to get the unnecessary equation parts to cancel out . C(graphite) + H2O CO(g) + H2(g) H = +131.3 kJ With the two equations packed together, notice the equations will cancel out and come out with the final equation. C(graphites) cancel out between the two equations . C(graphite) + H2O CO(g) + H2(g) CH4(g) C(graphite) + 2H2(g) Final Equation: CH4(g) + H2O CO + 3H2 H = +74.8 kJ + 131.3 kJ H = +131.3 kJ H = +74.8

4. Add the final enthalpies to the two fixed up equations and receive the enthalpy of the unknown equation: H = +201.1 kJ CH4(g) + H2O CO + 3H2 H = 201.1 kJ

Outside Links

Canagaratna, Sebastian G."Intensive and extensive: Underused concepts." J. Chem. Educ. 1992: 69, 957.

References

Atkins, Peter and Julio de Paula. Physical Chemistry for the Life Sciences. New York: Oxford University Press, 2006. Petrucci, et al. General Chemistry: Principles & Modern Applications: AIE (Hardcover). Upper Saddle River: Pearson/Prentice Hall, 2007. Senese, Fred. What are extensive and intensive properties? General Chemistry Online. 1997-2005. http://antoine.frostburg.edu/chem/senese/101/matter/faq/extensive-intensive.shtml C. Chieh, "Hess's Law" Cyberspace Chemistry 2008 http://www.science.uwaterloo.ca/~cchieh/cact/c120/hess.html

Contributors

Shelly Cohen (UCD)