Pressure Le Chatelier’s principle

Solution The expansion will result in a decrease in pressure. Le Chatelier s principle states that the reaction will shift to partially offset this decrease by increasing the number of moles present. There are 4 moles on the left side of the equation and 2 moles on the right, so the reaction will shift to the left. N2 and H2 concentration will increase. 

If a system containing one or more gases is at equilibrium and its volume is decreased, thereby increasing its total pressure, Le Chatelier s principle indicates that the system responds by shifting its equilibrium position to reduce the pressure. A system can reduce its pressure by reducing the total number of gas molecules (fewer molecules of gas... 

An account of the mechanism for creep in solids placed under a compressive hydrostatic suess which involves atom-vacancy diffusion only is considered in Nabano and Hemirg s (1950) volume diffusion model. The counter-movement of atoms and vacancies tends to relieve the effects of applied pressure, causing extension normal to the applied sU ess, and sluinkage in the direction of the applied sU ess, as might be anticipated from Le Chatelier s principle. The opposite movement occurs in the case of a tensile sU ess. The analysis yields the relationship... 

According to Le Chatelier s principle, conversion is increased by increasing the temperature and decreasing the pressure. Figure 6-3 shows the effect of temperature on the dehydrogenation of different light paraffins. ... 

Reality Check Note that the equilibrium partial pressure of HI is intermediate between its value before equilibrium was established (0.80 atm) and that immediately afterward (1.00 atm). This is exactly what Le Chatelier s principle predicts part of the added HI is consumed to re-establish equilibrium. 

Raising the temperature of liquid water raises its vapor pressure. This is in accord with Le Chatelier s Principle since heat is absorbed as the liquid vaporizes. This absorption of heat, which accompanies the change to the new equilibrium conditions, partially counteracts the temperature rise which caused the change. 

Can we predict the optimum conditions for a high yield of NH3 Should the system be allowed to attain equilibrium at a low or a high temperature Application of Le Chatelier s Principle suggests that the lower the temperature the more the equilibrium state will favor the production of NHS. Should we use a low or a high pressure The production of NH3 represents a decrease in total moles present from 4 to 2. Again Le Chatelier s Principle suggests use of pressure to increase concentration. But what about practicality At low temperatures reaction rates are slow. Therefore a compromise is necessary. Low temperature is required for a desirable equilibrium state and high temperature is necessary for a satisfactory rate. The compromise used industrially involves an intermediate temperature around 500°C and even then the success of the... 

Le Chatelier s Principle permits the chemist to make qualitative predictions about the equilibrium state. Despite the usefulness of such predictions, they represent far less than we wish to know. It is a help to know that raising the pressure will favor production of NH3 in reaction (10a). But how much will the pressure change favor NH3 production Will the yield change by a factor of ten or by one-tenth of a percent To control a reaction, we need quantitative information about equilibrium. Experiments show that quantitative predictions are possible and they can be explained in terms of our view of equilibrium on the molecular level. 

Note that there is no net change in the number of moles of gas in this equilibrium. Therefore, by Le Chatelier s principle, this reaction will be independent of external pressure (ignoring second-order effects due to gas imperfections). Under these conditions the N of the expl will... 

According to Le Chatelier s principle the equilibrium will be shifted to the right-hand side by high pressures and, since the reaction is exothermic, by low temperatures. Indeed early work by Haber showed that at 200 °C and 300 atmospheres pressure the equilibrium mix would contain 90% ammonia, whilst at the same pressure but at 700 °C the percentage of ammonia at equilibrium would be less than 5%. Unfortunately the activation energy is such that temperatures well in excess of 1000 °C are needed to overcome this energy barrier (Figure 4.1). The conclusion from this is that direct reaction is not a commercially viable option. 

It may be added here that Le Chatelier s principle is quite general in nature, and that its applicability is not restricted only to chemical equilibria. It can also be applied to physical equilibria, as for example, to explain qualitatively the effects of temperature and pressure on solubility or the effect of pressure on the melting of a solid. 

Le Chatelier s principle states that if a stress is applied to a system at equilibrium, the equilibrium will shift in a tendency to reduce that stress. A stress is something done to the system (not by the equilibrium reaction). The stresses that we consider are change of temperature, change of pressure, change of concentration(s), and addition of a catalyst. Let us consider the effect on a typical equilibrium by each of these stresses. 

Pressure affects the gases in a system much more than it affects the liquid or solids. We will investigate the same ammonia, hydrogen, nitrogen system discussed above. If the system is at equilibrium, what will an increase in pressure by the chemist do to the equilibrium The system will shift to try to reduce the stress, as required by Le Chatelier s principle. How can this system reduce its own pressure By reducing the total number of moles present. It can shift to the right to produce 2 mol of gas for every 4 mol used up ... 

The effect of external pressure on the rates of liquid phase reactions is normally quite small and, unless one goes to pressures of several hundred atmospheres, the effect is difficult to observe. In terms of the transition state approach to reactions in solution, the equilibrium existing between reactants and activated complexes may be analyzed in terms of Le Chatelier s principle or other theorems of moderation. The concentration of activated complex species (and hence the reaction rate) will be increased by an increase in hydrostatic pressure if the volume of the activated complex is less than the sum of the volumes of the reactant molecules. The rate of reaction will be decreased by an increase in external pressure if the volume of the activated complex molecules is greater than the sum of the volumes of the reactant molecules. For a decrease in external pressure, the opposite would be true. In most cases the rates of liquid phase reactions are enhanced by increased pressure, but there are also many cases where the converse situation prevails. 

Although it is not an explanation, Le Chatelier s principle is used to predict the effect of changes in conditions on the position of equilibrium. One statement of Le Chatelier s principle is If a system in equilibrium is subjected to a change which disturbs the equilibrium, the system responds in such a way as to counteract the effect of the change . The factors that may change the position of an equilibrium are concentration, temperature and pressure. 

Qualitatively, Le Chatelier s principle indicates that increasing the pressure will tend to decrease the fractional conversion of CH4 at equilibrium. At first it may therefore seem surprising that the reformer should be operated at a pressure as high as 30 bar. 

The reason for this lies in the relatively high cost of gas compression, which depends on the ratio of the inlet and outlet pressures. The methane feed to the reformer will probably be available at a pressure much above 1 bar and similarly with the steam. Le Chatelier s principle indicates also that excess steam, as used in practice, will favour a higher conversion of methane compared with the stoichiometric proportions of the reactants. The same conclusion follows quantitatively from Kpi for which the equation involves the total pressure P. 

A chemical equilibrium results when two exactly opposite reactions occur at the same place, at the same time, and with the same rate. An equilibrium constant expression represents the equilibrium system. Le Chatelier s principle describes the shifting of the equilibrium system due to changes in concentration, pressure, and temperature. 

At a given temperature, a reaction will reach equilibrium with the production of a certain amount of product. If the equilibrium constant is small, that means that not much product will be formed. But is there anything that can be done to produce more Yes, there is— through the application of Le Chatelier s principle. Le Chatelier, a French scientist, discovered that if a chemical system at equilibrium is stressed (disturbed) it will reestablish equilibrium by shifting the reactions involved. This means that the amounts of the reactants and products will change, but the final ratio will remain the same. The equilibrium may be stressed in a number of ways changes in concentration, pressure, and temperature. Many times the use of a catalyst is mentioned. However, a catalyst will have no effect on the equilibrium amounts, because it affects both the forward and reverse reactions equally. It will, however, cause the reaction to reach equilibrium faster. 

Le Chatelier s principle says that if an equilibrium system is stressed, it will reestablish equilibrium by shifting the reactions involved. A change in concentration of a species will cause the equilibrium to shift to reverse that change. A change in pressure or temperature will cause the equilibrium to shift to reverse that change. 

When the volume of a mixture of gases decreases, the pressure of the gases must increase. Le Chatelier s principle predicts a shift in equilihrium to relieve this change. Therefore, the shift must tend to reduce the pressure of the gases. Molecules striking the walls of a container cause gas pressure, so a reduction in gas pressure at constant temperature must mean fewer gas molecules. Consider the following reaction again. 

Le Chatelier s principle also predicts that the yield of ammonia is greater at higher pressures. High-pressure plants are expensive to huild and maintain, however. In fact, the first industrial plant that manufactured ammonia had its reaction vessel blow up. A German chemical engineer, Carl Bosch, solved this problem by designing a double-walled steel vessel that could operate at several hundred times atmospheric pressure. Modern plants operate at pressures in the range of 20 200 kPa to 30 400 kPa. 

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