CHEMISTRY GLOSSARY

Fahrenheit scale    →   Fahrenheitova skala

Fahrenheit scale is the temperature scale in which 212 degrees is the boiling point of water and 32 degrees is the freezing point of water. The scale was invented in 1714 by the German physicist G.D. Fahrenheit (1686-1736).

32 °F = 0 °C
212 °F = 100 °C
1 °F =(5/9) °C
T(°C) = (5/9)[T(°F) - 32]
T(°F) = (9/5)T(°C) + 32

chlorinity    →   klorinitet

Originally chlorinity (symbol Cl) was defined as the weight of chlorine in grams per kilogram of seawater after the bromides and iodides had been replaced by chlorides. To make the definition independent of atomic weights, chlorinity is now defined as 0.3285233 times the weight of silver equivalent to all the halides.

The Mohr-Knudsen titration method served oceanographers for more than 60 years to determine salinity from chlorinity. This modification of the Mohr method uses special volumetric glassware calibrated directly in chlorinity units. The Mohr method uses potassium chromate (K₂CrO₄) as an indicator in the titration of chloride ions chloride (plus a small amount of bromide and iodide) with a silver nitrate (AgNO₃) standard solution.

The other halides present are similarly precipitated.

A problem in the Mohr titration was that silver nitrate is not well suited for a primary standard. The Danish physicist Martin Knudsen (1871-1949) suggested that a standard seawater (Eau de mer Normale or Copenhagen Normal Water) be created and distributed to oceanographic laboratories throughout the world. This water was then used to standardize the silver nitrate solutions. In this way all chlorinity determinations were referred to one and the same standard which gave great internal consistency.

The relationship between chlorinity Cl and salinity S as set forth in Knudsen's tables is

In 1962, however, a better expression for the relationship between total dissolved salts and chlorinity was found to be

fugacity    →   fugacitet

Fugacity (f) is a thermodynamic function used in place of partial pressure in reactions involving real gases and mixtures. For a component of a mixture, it is defined by

where μ is the chemical potential.

The fugacity of a gas is equal to the pressure if the gas is ideal. The fugacity of a liquid or solid is the fugacity of the vapour with which it is in equilibrium. The ratio of the fugacity to the fugacity in some standard state is the activity.

electrode potential    →   elektrodni potencijal

Electrode potential is defined as the potential of a cell consisting of the electrode in question acting as a cathode and the standard hydrogen electrode acting as an anode. Reduction always takes place at the cathode, and oxidation at the anode. According to the IUPAC convention, the term electrode potential is reserved exclusively to describe half-reactions written as reductions. The sign of the half-cell in question determines the sign of an electrode potential when it is coupled to a standard hydrogen electrode.

Electrode potential is defined by measuring the potential relative to a standard hydrogen half cell

The convention is to designate the cell so that the oxidised form is written first. For example

The e.m.f. of this cell is

By convention, at p(H₂) = 101325 Pa and a(H⁺) = 1.00, the potential of the standard hydrogen electrode is 0.000 V at all temperatures. As a consequence of this definition, any potential developed in a galvanic cell consisting of a standard hydrogen electrode and some other electrode is attributed entirely to the other electrode

Kjeldahl’s method    →   Kjeldahlov postupak

Kjeldahl’s method is an analytical method for determination of nitrogen in certain organic compounds. The method was developed by the Danish chemist Johan Kjeldahl (1849-1900).

It involves addition of a small amount of anhydrous potassium sulphate to the test compound, followed by heating the mixture with concentrated sulphuric acid, often with a catalyst such as copper sulphate. As a result ammonia is formed. After alkalyzing the mixture with sodium hydroxyde, the ammonia is separated by distillation, collected in standard acid, and the nitrogen determined by back-titration.

1. Kjeldahl flask for decomposition (500 ml – macro or 100 ml - micro)
2. funnel for alkaline solution
3. Wagner tube (drop catcher)
4. condenser
5. absorption flask with known volume of standard acid

equilibrium constant    →   konstanta ravnoteže

The equilibrium constant (K) was originally introduced in 1863 by Norwegian chemists C.M. Guldberg and P. Waage using the law of mass action. For a reversible chemical reaction represented by the equation

chemical equilibrium occurs when the rate of the forward reaction equals the rate of the back reaction, so that the concentrations of products and reactants reach steady-state values.

The equilibrium constant is the ratio of chemical activities of the species A, B, C, and D at equilibrium.

To a certain approximation, the activities can be replaced by concentrations.

For gas reactions, partial pressures are used rather than concentrations

The units of K_p and K_c depend on the numbers of molecules appearing in the stoichiometric equation (a, b, c, and d).

The value equilibrium constant depends on the temperature. If the forward reaction is exothermic, the equilibrium constant decreases as the temperature rises. The equilibrium constant shows the position of equilibrium. A low value of K indicates that [C] and [D] are small compared to [A] and [B]; i.e. that the back reaction predominates.

The equilibrium constant is related to Δ_rG°, the standard Gibbs free energy change in the reaction, by

Nernst’s electrode potential equation    →   Nernstova jednadžba za elektrodni potencijal

For general reaction of some redox system

dependence of electrode potential of redox system upon activity of oxidised and reduced form in solution is described in Nernst’s equation for electrode potential:

where E = to electrode potential of redox system

E° = standard electrode potential of redox system

R = universal gas constant

T = thermodymical temperature

F = Faraday’s constant

z = number of electrons exchanged in redox reaction

a_O = activity of oxidised form

a_R = activity of reduced form

n = stechiometrical coefficient of oxidised form

m = stechiometrical coefficient of reduced form

normal conditions    →   normalni uvjeti

Gas is under normal (or standard) conditions when: p₀ = 10⁵ Pa and T₀ = 273.15 K (0 °C). IUPAC recommends that the former use of the pressure of 1 atm as standard pressure (equivalent to 101 325 Pa) should be discontinued. At these conditions, the molar volume of gas V_m0 is 0.022 711 m³ (22.711 L).

potentiometric titration    →   potenciometrijska titracija

Potentiometric titration is a volumetric method in which the potential between two electrodes is measured (referent and indicator electrode) as a function of the added reagent volume. Types of potentiometric titrations for the determination of analytes in photoprocessing solutions include acid-base, redox, precipitation, and complexometric.

Potentiometric titrations are preferred to manual titrations, since they are more accurate and precise. They are also more easily adapted to automation, where automated titration systems can process larger volumes of samples with minimal analyst involvement.

A titration curve has a characteristic sigmoid curve. The part of the curve that has the maximum change marks the equivalence point of the titration. The first derivative, ΔE/ΔV, is the slope of the curve, and the endpoint occurs at the volume, V', where ΔE/ΔV has the maximum value.

practical salinity    →   praktični salinitet

Practical salinity S_P is defined on the Practical Salinity Scale of 1978 (PSS-78) in terms of the conductivity ratio K₁₅ which is the electrical conductivity of the sample at temperature t₆₈ = 15 °C and pressure equal to one standard atmosphere, divided by the conductivity of a standard potassium chloride (KCl) solution at the same temperature and pressure. The mass fraction of KCl in the standard solution is 0.0324356 (32.4356 g of KCl in 1 kg of solution). When K₁₅ = 1, the Practical Salinity P S is by definition 35. The conductivity of that reference solution is C(35,1568,0) = 42.914 mS/cm = 4.2914 S/m (Siemens per meter). Note that Practical Salinity is a unit-less quantity. Though sometimes convenient, it is technically incorrect to quote Practical Salinity in "psu". When K₁₅ is not unity, S_P and K₁₅ are related by the PSS-78 equation

At a temperature of t₆₈ = 15 °C, R_t is simply K₁₅ and Practical Salinity S_P can be determined from the above equation. For temperatures other than t₆₈ = 15 °C, Practical Salinity S_P is given by the following function of R_t (k = 0.0162)