# 13.3 Shifting equilibria: le châtelier’s principle  (Page 3/10)

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Because there is no change in the total number of molecules in the system during reaction, a change in pressure does not favor either formation or decomposition of gaseous nitrogen monoxide.

## Effect of change in temperature on equilibrium

Changing concentration or pressure perturbs an equilibrium because the reaction quotient is shifted away from the equilibrium value. Changing the temperature of a system at equilibrium has a different effect: A change in temperature actually changes the value of the equilibrium constant. However, we can qualitatively predict the effect of the temperature change by treating it as a stress on the system and applying Le Châtelier's principle.

When hydrogen reacts with gaseous iodine, heat is evolved.

${\text{H}}_{2}\left(g\right)+{\text{I}}_{2}\left(g\right)⇌2\text{HI}\left(g\right)\phantom{\rule{5em}{0ex}}\text{Δ}H=-9.4\phantom{\rule{0.2em}{0ex}}\text{kJ}\phantom{\rule{0.2em}{0ex}}\left(\text{exothermic}\right)$

Because this reaction is exothermic, we can write it with heat as a product.

${\text{H}}_{2}\left(g\right)+{\text{I}}_{2}\left(g\right)⇌\text{2HI}\left(g\right)+\text{heat}$

Increasing the temperature of the reaction increases the internal energy of the system. Thus, increasing the temperature has the effect of increasing the amount of one of the products of this reaction. The reaction shifts to the left to relieve the stress, and there is an increase in the concentration of H 2 and I 2 and a reduction in the concentration of HI. Lowering the temperature of this system reduces the amount of energy present, favors the production of heat, and favors the formation of hydrogen iodide.

When we change the temperature of a system at equilibrium, the equilibrium constant for the reaction changes. Lowering the temperature in the HI system increases the equilibrium constant: At the new equilibrium the concentration of HI has increased and the concentrations of H 2 and I 2 decreased. Raising the temperature decreases the value of the equilibrium constant, from 67.5 at 357 °C to 50.0 at 400 °C.

Temperature affects the equilibrium between NO 2 and N 2 O 4 in this reaction

${\text{N}}_{2}{\text{O}}_{4}\left(g\right)⇌2{\text{NO}}_{2}\left(g\right)\phantom{\rule{5em}{0ex}}\text{Δ}H=57.20\phantom{\rule{0.2em}{0ex}}\text{kJ}$

The positive Δ H value tells us that the reaction is endothermic and could be written

$\text{heat}+{\text{N}}_{2}{\text{O}}_{4}\left(g\right)⇌2{\text{NO}}_{2}\left(g\right)$

At higher temperatures, the gas mixture has a deep brown color, indicative of a significant amount of brown NO 2 molecules. If, however, we put a stress on the system by cooling the mixture (withdrawing energy), the equilibrium shifts to the left to supply some of the energy lost by cooling. The concentration of colorless N 2 O 4 increases, and the concentration of brown NO 2 decreases, causing the brown color to fade.

## Catalysts do not affect equilibrium

As we learned during our study of kinetics, a catalyst can speed up the rate of a reaction. Though this increase in reaction rate may cause a system to reach equilibrium more quickly (by speeding up the forward and reverse reactions), a catalyst has no effect on the value of an equilibrium constant nor on equilibrium concentrations.

The interplay of changes in concentration or pressure, temperature, and the lack of an influence of a catalyst on a chemical equilibrium is illustrated in the industrial synthesis of ammonia from nitrogen and hydrogen according to the equation

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Acquah