The alkali metals have the high thermal and electrical conductivity, lustre, ductility, and malleability that are characteristic of metals. Each alkali metal atom has a single electron in its outermost shell. This valence electron is much more weakly bound than those in inner shells. As a result, the alkali metals tend to form singly charged positive ions (cations) when they react with nonmetals. The compounds that result have high melting points and are hard crystals that are held together by ionic bonds (resulting from mutually attractive forces that exist between positive and negative electrical charges). In the metallic state, either pure or in alloys with other alkali metals, the valence electrons become delocalized and mobile as they interact to form a half-filled valence band. As with other metals, such a partially filled valence band is a conduction band and is responsible for the valence properties typical of metals. In passing from lithium to francium, the single electron tends to be less strongly held. Generally, the energy necessary to remove the outermost electron from the atoms of an element, the ionization energy, decreases in the periodic table toward the left and downward in each vertical file, with the result that the most easily ionizable element in the entire table is francium, followed closely by cesium. The alkali metals, which make up the extreme left-hand file, have ionization energies ranging from 124.3 kilocalories per mole (kcal/mole) in lithium to 89.7 kcal/mole in cesium (omitting the rare radioactive element francium). The alkaline-earth metals, the next group to the right, have higher ionization energies ranging from 214.9 in beryllium to 120.1 kcal/mole in barium.
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The electronegativity scale of the elements compares the ability of the atoms of the various elements to attract electrons to themselves. In the periodic table the electronegativities range from 0.7 for cesium, the least electronegative of the elements, to 4.0 for fluorine, the most electronegative. Metals are ordinarily considered to be those elements having values less than 2.0 on the electronegativity scale. As a group the alkali metals are the least electronegative of the elements, ranging from 0.7 to 1.0 on the scale, while the alkaline earths, the next group on the table, have electronegativities ranging from about 0.9 to 1.5.
The table summarizes the important physical and thermodynamic properties of the alkali metals. At atmospheric pressure these metals are all characterized by a body-centred cubic crystallographic arrangement (a standard pattern of atoms in their crystals), with eight nearest neighbours to each atom. The closest distance between atoms, a characteristic property of crystals, increases with increasing atomic weight of the alkali metal atoms. As a group, the alkali metals have a looser crystallographic arrangement than any of the other metallic crystals, and cesium—because of its greater atomic weight—has an interatomic distance that is greater than that of any other metal.
|atomic weight (or stablest isotope)||6.941||22.99||38.098||86.468||132.905||223|
|colour of element||silver||silver||silver||silver||silver||—|
|melting point (°C)||180.5||97.72||63.38||39.31||28.44||27|
|boiling point (°C)||1,342||883||759||688||671||677|
|density at 20 °C (grams per cubic centimetre)||0.534||0.971||0.862||1.532||1.873||—|
|volume increase on melting (percent)||1.51||2.63||2.81||2.54||2.66||—|
|mass number of most common isotopes (terrestrial abundance, percent)||6 (7.59), 7 (92.41)||23 (100)||39 (93.2581), 40 (0.0117), 41 (6.7302)||85 (72.17), 87 (27.83)||133 (100)||—|
|colour imparted to flame||red||yellow||violet||yellow violet||blue||—|
|main spectral emission lines (wavelength, angstroms)||6,708; 6,104||5,890; 5,896||7,699; 7,665||4,216; 4,202||4,593; 4,555||—|
|heat of fusion (calories per mole/kilojoules per mole)||720 (3)||621 (2.6)||557 (2.33)||523 (2.19)||500 (2.09)||500 (2)|
|specific heat (joules per gram kelvin)||3.582||1.228||0.757||0.363||0.242||—|
|electrical resistivity at 293–298 K (microhm-centimetres)||9.5||4.9||7.5||13.3||21||—|
|magnetic susceptibility (cgs units)||14.2 (10−6)||16 (10−6)||20.8 (10−6)||17 (10−6)||29 (10−6)||—|
|crystal structure||body-centred cubic||body-centred cubic||body-centred cubic||body-centred cubic||body-centred cubic||—|
|radius: atomic (angstroms)||1.67||1.9||2.43||2.65||2.98||—|
|radius: ionic (+1 ion, angstroms)||0.9||1.16||1.52||1.66||1.81||1.94|
|radius: metallic (angstroms, 12-coordinate)||1.57||1.91||2.35||2.5||2.72||2.8|
|first ionization energy (kilojoules per mole)||520.2||495.8||418.8||403||375.7||380|
|oxidation potential for oxidation from the 0 to +1 oxidation state at 25 °C (volts)||3.04||2.71||2.93||2.92||2.92||2.92|
Vapour-pressure data for the alkali metals and for two alloys formed between elements of the group show that the vapour pressures increase in regular fashion with increasing atomic weight. Cesium is the most volatile of the alkali metals, with a boiling point of 671 °C (1,240 °F). The boiling points of the alkali metals decrease in regular fashion as the atomic numbers increase, with the highest, 1,317 °C (2,403 °F), being that of lithium.
The melting points of the alkali metals as a group are lower than those of any other nongaseous group of the periodic table, ranging between 179 °C (354 °F) for lithium and 28.5 °C (83.3 °F) for cesium. Among the metallic elements, only mercury has a lower melting point (−38.9 °C, or −38.02 °F) than cesium. The low melting points of the alkali metals are a direct result of the large interatomic distances in their crystals and the weak bond energies associated with such loose arrays. These same factors are responsible for the low densities, low heats of fusion, and small changes in volume upon fusion of the metals. Lithium, sodium, and potassium are less dense than water.
The large size of an alkali metal atom (and the resulting low density of the metal) results from the presence of only one, weakly bound electron in the large outer s-type orbital. Upon going from the noble-gas configuration of argon (atomic number 18) to potassium (atomic number 19), the added electron goes into the large 4s orbital rather than the smaller 3p orbital. When, however, potassium, rubidium, or cesium metals are subjected to increasing pressure (up to one-half million atmospheres or more), a number of phase transitions occur. Ultimately, occupation of a d-type orbital becomes preferred over that of the s-orbital, with the result that these alkali metals resemble transition metals. Under such circumstances, alloys with transition metals (such as iron) can form, a result that does not occur at low pressures. It has been proposed that the lower-than-expected density of Earth’s core may be the result of the formation of a potassium-iron alloy under the extreme pressures that occur there.
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The alkali metals have played an important role in quantum physics. Some alkali metal isotopes, such as rubidium-87, are bosons. Dilute atomic gases of such alkali metal isotopes, confined by magnetic fields or “laser mirrors” and cooled to temperatures near absolute zero, form Bose-Einstein condensates. In this state, the cluster of atoms is in a single quantum state and exhibits macroscopic behaviours normally seen only with atomic-sized particles. These include interference effects and coherent motion of the entire “cloud” of atoms.