Thermodynamic laws are the foundation of the science of thermodynamics:
First law: The internal energy of an isolated system is constant; if energy is supplied to the system in the form of heat dq and work dw, then the change in energy dU = dq + dw.
Second law: No process is possible in which the only result is the transfer of heat from a reservoir and its complete conversion to work.
Third law: The entropy of a perfect crystal approaches zero as the thermodynamic temperature approaches zero.
Van der Waals’ equation is an equation of state for real fluids which takes the form:
where p is pressure, Vm is molar volume, T is temperature, R is the molar gas constant, and a and b are characteristic parameters of the substance which describe the effect of attractive and repulsive intermolecular forces.
Van’t Hoff equation is the equation expressing the temperature dependence on the equilibrium constant K of a chemical reaction:
where ΔrH° is the standard enthalpy of reaction, R the molar gas constant, and T the temperature.
Water ion product (Kw) is a concentration product of hydrogen and hydroxide ions. For the reaction:
the equilibrium expression would be:
Note that all pure liquid terms are omitted, hence H2O does not appear in the denominator. At 25 °C, Kw = 1.0×10-14 mol2dm-6 = (Ka)(Kb)
Work is the energy required to move an object against an opposing force. Work is usually expressed as a force times a displacement.
When a constant force F acts on a point-like object while the object moves through a displacement s, the force does work W on the object. If force and displacement are at a constant angle Θ to each other, the work is expressed by the scalar product of these two vectors:
When the force F on a point-like object is not constant that is, it depends on the position of the object, the work done by force while object moves from initial position with coordinates (xi, yi, zi) to final position with coordinates (xf, yf, zf)is given by expression:
Where Fx, Fy and Fz are scalar components of the force.
SI unit for work is joule (J); 1 J = 1 Nm = 1 kg m2 s-2. The electron-volt (eV) is commonly used in atomic and nuclear physics.
The carbon dioxide ion selective electrode uses a gas-permeable membrane to separate the sample solution from the electrode internal solution. Dissolved carbon dioxide in the sample solution diffuses through the membrane until an equilibrium is reached between the partial pressure of CO2 in the sample solution and the CO2 in the internal filling solution. In any given sample the partial pressure of carbon dioxide will be proportional to the concentration of carbon dioxide. The diffusion across the membrane affects the level of hydrogen ions in the internal filling solution:
The hydrogen level of the internal filling solution is measured by the pH electrode located behind the membrane. The internal filling solution contains a high concentration of sodium bicarbonate (e.g. 0.1 mol/L NaHCO3) so that the bicarbonate level can be considered constant.
The Heyrovsky-Ilkovic equation describes the entire current-potential curve (polarographic wave) of a reversible redox system in polarography
where R is the gas constant, T is the absolute temperature, F is the Faraday constant, n denotes the number of electrons taking part in the electrode reaction. E1/2 is a unique potential (for a given reaction and supporting electrolyte) termed the half-wave potential.
In order to obtain E1/2 from the above equation, we plot a graph of ln[(id-i)/i] against E. The intercept on the x-axis gives then an accurate value of E1/2. The slope of the obtained straight line is equal to nF/RT from which n is determined.
Generalic, Eni. "Planckova konstanta." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
Glossary
Periodic Table