Physical chemistry is the study of macroscopic and microscopic phenomena in chemical systems in terms of the principles, practices, and concepts of physics such as motion, energy, force, time, thermodynamics, quantum chemistry, statistical mechanics, analytical dynamics and chemical equilibria. Physical chemistry, in contrast to chemical physics, is predominantly (but not always) a supra-molecular science, as the majority of the principles on which it was founded relate to the bulk rather than the molecular or atomic structure alone (for example, chemical equilibrium and colloids). Some of the relationships that physical chemistry strives to understand include the effects of:
Intermolecular forces that act upon the physical properties of materials (plasticity, tensile strength, surface tension in liquids). Reaction kinetics on the rate of a reaction. The identity of ions and the electrical conductivity of materials. Surface science and electrochemistry of cell membranes. Interaction of one body with another in terms of quantities of heat and work called thermodynamics. Transfer of heat between a chemical system and its surroundings during change of phase or chemical reaction taking place called thermochemistry Study of colligative properties of number of species present in solution. Number of phases, number of components and degree of freedom (or variance) can be correlated with one another with help of phase rule. Reactions of electrochemical cells. Behaviour of microscopic systems using quantum mechanics and macroscopic systems using statistical thermodynamics. Calculation of the energy of electron movement in molecules and metal complexes.
Key concepts The key concepts of physical chemistry are the ways in which pure physics is applied to chemical problems. One of the key concepts in classical chemistry is that all chemical compounds can be described as groups of atoms bonded together and chemical reactions can be described as the making and breaking of those bonds. Predicting the properties of chemical compounds from a description of atoms and how they bond is one of the major goals of physical chemistry. To describe the atoms and bonds precisely, it is necessary to know both where the nuclei of the atoms are, and how electrons are distributed around them.
Disciplines Quantum chemistry, a subfield of physical chemistry especially concerned with the application of quantum mechanics to chemical problems, provides tools to determine how strong and what shape bonds are, how nuclei move, and how light can be absorbed or emitted by a chemical compound. Spectroscopy is the related sub-discipline of physical chemistry which is specifically concerned with the interaction of electromagnetic radiation with matter. Another set of important questions in chemistry concerns what kind of reactions can happen spontaneously and which properties are possible for a given chemical mixture. This is studied in chemical thermodynamics, which sets limits on quantities like how far a reaction can proceed, or how much energy can be converted into work in an internal combustion engine, and which provides links between properties like the thermal expansion coefficient and rate of change of entropy with pressure for a gas or a liquid. It can frequently be used to assess whether a reactor or engine design is feasible, or to check the validity of experimental data. To a limited extent, quasi-equilibrium and non-equilibrium thermodynamics can describe irreversible changes. However, classical thermodynamics is mostly concerned with systems in equilibrium and reversible changes and not what actually does happen, or how fast, away from equilibrium. Which reactions do occur and how fast is the subject of chemical kinetics, another branch of physical chemistry. A key idea in chemical kinetics is that for reactants to react and form products, most chemical species must go through transition states which are higher in energy than either the reactants or the products and serve as a barrier to reaction. In general, the higher the barrier, the slower the reaction. A second is that most chemical reactions occur as a sequence of elementary reactions, each with its own transition state. Key questions in kinetics include how the rate of reaction depends on temperature and on the concentrations of reactants and catalysts in the reaction mixture, as well as how catalysts and reaction conditions can be engineered to optimize the reaction rate. The fact that how fast reactions occur can often be specified with just a few concentrations and a temperature, instead of needing to know all the positions and speeds of every molecule in a mixture, is a special case of another key concept in physical chemistry, which is that to the extent an engineer needs to know, everything going on in a mixture of very large numbers (perhaps of the order of the Avogadro constant, 6 × 1023) of particles can often be described by just a few variables like pressure, temperature, and concentration. The precise reasons for this are described in statistical mechanics, a specialty within physical chemistry which is also shared with physics. Statistical mechanics also provides ways to predict the properties we see in everyday life from molecular properties without relying on empirical correlations based on chemical similarities.
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