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In 1884, Jacobus van 't Hoff proposed the Van 't Hoff equation describing the temperature dependence of the equilibrium constant for a reversible reaction: = where ΔU is the change in internal energy, K is the equilibrium constant of the reaction, R is the universal gas constant, and T is thermodynamic temperature.
If a dynamic equilibrium is disturbed by changing the conditions, the position of equilibrium moves to partially reverse the change. For example, adding more S (to the chemical reaction above) from the outside will cause an excess of products, and the system will try to counteract this by increasing the reverse reaction and pushing the ...
The concept of a transition state has been important in many theories of the rates at which chemical reactions occur. This started with the transition state theory (also referred to as the activated complex theory), which was first developed around 1935 by Eyring, Evans and Polanyi, and introduced basic concepts in chemical kinetics that are still used today.
The reversible reaction N 2 O 4 (g) ⇌ 2NO 2 (g) is endothermic, so the equilibrium position can be shifted by changing the temperature. When heat is added and the temperature increases, the reaction shifts to the right and the flask turns reddish brown due to an increase in NO 2. This demonstrates Le Chatelier's principle: the equilibrium ...
However, all reactions can be represented as a series of elementary reactions and, if the mechanism is known in detail, the rate equation for each individual step is given by the expression so that the overall rate equation can be derived from the individual steps. When this is done the equilibrium constant is obtained correctly from the rate ...
Consequently, the object is in a state of static mechanical equilibrium. In classical mechanics, a particle is in mechanical equilibrium if the net force on that particle is zero. [1]: 39 By extension, a physical system made up of many parts is in mechanical equilibrium if the net force on each of its individual parts is zero. [1]: 45–46 [2]
In such a case, it is likely that the mechanism of the reaction changes upon adding a different substituent. Other deviations from linearity may be due to a change in the position of the transition state. In such a situation, certain substituents may cause the transition state to appear earlier (or later) in the reaction mechanism. [7] [page ...
The reaction yield stabilizes at equilibrium but can be increased by removing the product from the reaction mixture or changed by increasing the temperature or pressure. A change in the concentrations of the reactants does not affect the equilibrium constant but does affect the equilibrium position.