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Chapter: Modern Analytical Chemistry: Equilibrium Chemistry

Reversible Reactions and Chemical Equilibria

Berthollet “knew” that a reaction between Na2CO3 and CaCl2 goes to comple- tion, forming NaCl and a precipitate of CaCO3 as products.

Reversible Reactions and Chemical Equilibria

In 1798, the chemist Claude Berthollet (1748–1822) accompanied a French military expedition to Egypt. While visiting the Natron Lakes, a series of salt water lakes carved from limestone, Berthollet made an observation that contributed to an im- portant discovery. Upon analyzing water from the Natron Lakes, Berthollet found large quantities of common salt, NaCl, and soda ash, Na2CO3, a result he found sur- prising. Why would Berthollet find this result surprising and how did it contribute

Berthollet “knew” that a reaction between Na2CO3 and CaCl2 goes to comple- tion, forming NaCl and a precipitate of CaCO3 as products.

Na2CO3 + CaCl2 → 2NaCl + CaCO3

Understanding this, Berthollet expected that large quantities of NaCl and Na2CO3 could not coexist in the presence of CaCO3. Since the reaction goes to completion, adding a large quantity of CaCl2 to a solution of Na2CO3 should produce NaCl and CaCO3, leaving behind no unreacted Na2CO3. In fact, this result is what he ob- served in the laboratory. The evidence from Natron Lakes, where the coexistence of NaCl and Na2CO3 suggests that the reaction has not gone to completion, ran counter to Berthollet’s expectations. Berthollet’s important insight was recognizing that the chemistry occurring in the Natron Lakes is the reverse of what occurs in the laboratory.

CaCO3 + 2NaCl → Na2CO3 + CaCl2

Using this insight Berthollet reasoned that the reaction is reversible, and that the relative amounts of “reactants” and “products” determine the direction in which the reaction occurs, and the final composition of the reaction mixture. We recog- nize a reaction’s ability to move in both directions by using a double arrow when writing the reaction.

Na2CO3 + CaCl2 < = = = = > 2NaCl + CaCO3

Berthollet’s reasoning that reactions are reversible was an important step in understanding chemical reactivity. When we mix together solutions of Na2CO3 and CaCl2, they react to produce NaCl and CaCO3. If we monitor the mass of dissolved Ca2+ remaining and the mass of CaCO3 produced as a function of time, the result will look something like the graph in Figure 6.2. At the start of the reaction the mass of dissolved Ca2+ decreases and the mass of CaCO3 in- creases. Eventually, however, the reaction reaches a point after which no further changes occur in the amounts of these species. Such a condition is called a state of equilibrium.


Although a system at equilibrium appears static on a macroscopic level, it is important to remember that the forward and reverse reactions still occur. A reac- tion at equilibrium exists in a “steady state,” in which the rate at which any species forms equals the rate at which it is consumed.

 

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