Hydrides

Metallic Saline (salt-like) Molecular Polymeric

Interstitial metal hydrides

Hydrogen atoms are small enough to occupy the interstitial holes in a metal lattice The absorption of H2 by metal Ex : TiH1.7, HfH1.98 and HfH2.10 etc

Saline (salt like) hydrides

when hydrogen reacts with very reactive metals.
metals of group 1 & 2 heated with H2 2Li(s) + H2(g) 2LiH(s) Ca(s) + H2(g) CaH2(s)

Products : white, solid, high m.p

Ex. LiH, mp . 953 K; NaH, mp . 1073K

The reactivity of the group 1 hydrides increases with an increase in atomic number and ionic size of the metal; Values of fHo become less negative, with that of LiH being significantly more negative than those of the other alkali metal hydrides React immediately with protic solvents (H2O, NH3 or EtOH)
H- is extremely strong base

Uses of saline hydrides

Deprotonating agents Reducing agents

Molecular hydrides
- covalent and complex hydrides -

Covalent hydrides
when hydrogen reacts with nonmetals. In most covalent hydrides, hydrogen has an oxidation number of +1.
F2(g) + H2(g) 2HF(g) DHrxn = -546 kJ

With p-blocks elements of group 13 -17 (except Al and Bi, because thermally unstable ) Versatile Has simple structure Ex. BH3 (in gas to be B2H6)

Covalent hydrides
1. 2. 3. 4. 5. 6. Neutral hydrides like XH4 compounds of group 14 such as CH4, SiH4 and all hydrocarbons Basic hydrides like the XH3 compounds of group 15 NH3 and PH3, AsH3, SbH3, BiH3 Weakly acidic or amphoteric XH2 compounds fo group 16 such as H2O and H2S Strongly acidic hydrides like HX compounds of group 17 such as HI, HCl, HBr Hydridic complexes of hydrogen such as LiAlH4 and NaBH4 Numerous covalent hydrides of boron (borane B2H6, tetraborane B4H10, pentaborane B5H11

Complex hydrides
- for d blocks Molecular hydrido complexes are known for d-block metals from groups 710 (excluding Mn) and counter-ions are commonly from group 1 or 2, e.g. K2ReH9, Li4RuH6, Na3RhH6, Mg2RuH4, Na3OsH7 and Ba2PtH6, etc

Polymeric hydrides

Hydrogen Bonds
A H-bond is an
attractive interaction between a hydrogen atom bonded to a very electronegative atom (O, N, F) and an unshared electron pair on another electronegative atom.

Hydrogen Bonds
Evidence for H-bonds
Unusually high mps and bps, latent heats of vapourisation and fusion of NH3, HF and H2O implies extra interaction in the liquid and solid state
X-ray diffraction studies give X---Y distances shorter than expected when a H-bond exists Neutron diffraction studies allows the position of H atoms to be determined

IR studies show that when X-H is involved in H-bonding with element Y, the characteristic IR stretching frequency of XH is lowered because the bond is weakened

Hydrogen Bonds
Consider the boiling points of group 14 hydrides

Hydrogen Bonds
Consider the bp of group 15, 16 and 17 hydrides

Importance of H-bonds seen in :

Structure and properties of water and ice Double helix structure of DNA Crucial three dimensional shape of large proteins and enzymes Life as we know it could not exist without Hbonds

Hydrogen Bonds in DNA

02. Group 1: The Alkali Metals

Overview
Occurrence, extraction Isotopes Properties Uses Reactivity Halides Oxides and hydroxides Salts of oxoacids Aqueous solution chemistri Non-aqueous coordination chemistry

Group 1A
Of these alkali metals, francium (Fr) is a very rare, radioactive and unstable element. This makes it difficult to study.

Reactivity increases

Size of the atom increases

Elements of group 1A
Discovery take a look at : http://cnx.org/content/m31909/latest/#id1170867062 372

http://cnx.org/content/m31909/latest/#id1170867062372

Abundant

Occurrence
The abundant in the earths biosphere Na = 2.6% and K = 2.4 %, but do not occur naturally in the elemental state Main sources rock salt NaCl, KCl, KCl.MgCl2.6H2O, borax (Na2[B4O5(OH)4].8H2O, NaNO3

Extraction
SODIUM (Na) Down process producing Na commercially from NaCl molten NaCl is electrolysed; CaCl2 is added to reduce the operating temperature to about 870 K, since pure NaCl melts at 1073 K.

Extraction

Li electrolysis process from LiCl LiCl is obtained by heating spodumene (LiAlSi2O6) with CaO LiOH LiCl K electrolysis from KCl Rb and Cs electrolysis from RbCl and CsCl or reduction of RbOH and CsOH Na, K, Rb and Cs can be obtained also by thermal decomposition of their azides

Isotopes

General properties
Alkali metals are the largest elements in their respective periods and their valence electron configuration is ns1. The valence e- is relatively far from the nucleus, resulting in weak metallic bonding. Alkali metals are different to typical (transition) metals, such as iron and copper. Unlike typical metals, alkali metals:
are soft and can be cut by a knife softness increases down the group; have a low density lithium, sodium and potassium float on water; have low melting and boiling points.

However, alkali metals do share a few properties with typical metals, because:
they are good conductors of heat and electricity; they are shiny this is only seen when they are freshly cut. The metals Li, Na, K and Rb are silvery-white, but Cs has a golden-yellow cast.

Trends in density
The alkali metals generally become more dense down the group, but the trend is not perfect because potassium is less dense than sodium. Element Density (g/dm3)

lithium
sodium potassium rubidium caesium

0.53
0.97 0.86 1.53 1.87

Water has a density of 1 g/dm3. Lithium, sodium and potassium are all less dense than water and so will float.

Trends in melting point

The melting point of alkali metals decreases down the group.

Element
lithium sodium potassium rubidium caesium

Melting point (C)

181 98 64 39 28

Melting points are lower than for typical (transition) metals, because alkali metals only have 1 electron in their outer shell. Not much energy is needed for this electron to be lost.

Flame property

Li

Na

Rb

Cs

When the salt of an alkali metal is treated with concentrated HCl (giving a volatile metal chloride) and is heated strongly in the non-luminous Bunsen flame, a characteristic flame colour is observed (Li, crimson; Na, yellow; K, lilac; Rb, red-violet; Cs, blue) and this flame test is used in qualitative analysis to identify the M+ ion. In quantitative analysis, use is made of the characteristic atomic spectrum in flame photometry and atomic absorption spectroscopy.

Group 1A(1): The Alkali Metals

Family Portrait

KEY ATOMIC PROPERTIES, PHYSICAL PROPERTIES, AND REACTIONS

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Uses - Lithium
lithium stearate is mixed with oils to make all-purpose and high-temperature lubricants lithium hydroxide is used to absorb carbon dioxide in space vehicles lithium is alloyed with aluminium, copper, manganese, and cadmium to make high perfomance alloys for aircraft Bahnmetall consists of lead containing 0.04% lithium, 0.7% calcium and 0.6% sodium is harder than pure lead and was used for railroad car bearings in Germany. compounds such as LiAlH4 and organolithium reagents (LiMe, LiPh, etc.) are very important as reagents in organic chemistry lithium metal has the highest specific heat of any solid element and so heat transfer applications various nuclear applications lithium is sometimes used as battery anode material (high electrochemical potential) and lithium compounds are used in dry cells and storage batteries lithium is used in the manufacture of special high strength glasses and ceramics sometimes, lithium-based compounds such as lithium carbonate (Li2CO3) are used as drugs to treat manic-depressive disorders.

Uses - Sodium
Sodium metal is used in the preparation of tetraethyl lead, PbEt4, an important antiknock reagent in leaded petrol (gasoline) - fortunately being phased out in many countries because of lead pollution problems sodium metal is used in the preparation of titanium metal from TiCl4 the metal is used in the manufacture of sodamide, sodium cyanide, sodium peroxide, and sodium hydride the metal is used in the reduction of organic esters, and in the preparation of organic compounds the alloy with potassium, NaK, is an important heat transfer agent and a good chemical reducing agent (as some proportions of Na and K are liquid at room temperature). sodium compounds including "common salt" (sodium chloride, NaCl), "soda ash" (sodium carbonate, Na2CO3), "baking soda" (sodium bicarbonate, NaHCO3, "bicarb"), and "caustic soda" (sodium hydroxide, NaOH), are important to the paper, glass, soap, textile, petroleum, chemical, and metal industries sodium vapour is used in lamps for street lighting, it adds a bright orange glow to the light

Uses - Potassium
The superoxide KO2 is used in breathing apparatus where moisture in the breath and carbon dioxide reacts with it to release oxygen [2KO2 + H2O + 2CO2 2KHCO3 + O2 ] the alloy of potassium with sodium (NaK) is used as a heat-transfer medium in nuclear reactors. The alloy is liquid at ambient temperature and is a good reducing agent in the chemistry laboratory fertilizers - usually as the chloride, sulphate, nitrate, or carbonate possium nitrate, KNO3, and potassium chlorate, KClO3, are used in fireworks potassium bromide, KBr, was used as an antaphrodisiac potassium permanganate, KMnO4, is an important oxidizing agent low-sodium salt potassium hydroxide is used in the preparation of potassium phosphates for liquid detergents

Uses - Rubidium
rubidium is easily ionized, and so has possible use in "ion engines" for space vehicles (but caesium is somewhat more efficient) used as a "getter" in vacuum tubes photocell component used for making special glasses RbAg4I5 has the highest room temperature conductivity of any known ionic crystal. At ambient temperature, its conductivity is about the same as dilute sulphuric acid, suggesting uses in thin film batteries

Uses Cs & Fr
Caesium : relatively few uses and is not often encountered. Some uses include:
used as a catalyst in the hydrogenation of a few organic compounds the metal can be used in ion propulsion systems. Although not usable in the earth's atmosphere, 1 kg of caesium in outer space could propel a vehicle 140 times as far as the burning of the same amount of any known liquid or solid. It is more efficient than rubidium. used in atomic clocks because of its high oxygen affinity, the metal is used as a "getter" in electron tubes used in photoelectric cells and vacuum tubes IR lamps

Francium has no uses