Alkali metals and their properties

A GRADUATION PROJECT REPORT

Submitted to Chemistry Department of College of Science in partial fulfillment
of the requirements for the degree of B.Sc. of Chemistry science

Submitted by:
Muhsan Mirza Darwish

Supervised by:
Dr. Mohammed Mahmoud Molla-Babaker

April 2024
 DEDICATION

I dedicate this modest effort to.... My Parents.... Allah extended

their lives.
Everyone who encouraged me and give me the aid in every
possible way in order to make this work have the present picture.
Our friends and the students of U0Z hopefully our work will help
them to have better idea about future researches.
My supervisor Dr. Mohammed Mahmoud for his significant
effort.

I
 ACKNOWLEDGMENT

All praises to Allah the Almighty, the most Merciful, and the most
Gracious.
I would like to express deepest thanks and gratitude to my
supervisor Dr. Mohammed Mahmoud his fruitful facilities.
Deepest thanks are due to the Dean of the College of Science /
University of Zakho. Also, I would like to thanks the Head of
Chemistry Department and all the staff members of the Department
of Chemistry / College of Science.
Special thank...

II
 Table of Contents
DEDICATION................................................................................................... I

ACKNOWLEDGMENT ................................................................................. II

List of tables ................................................................................................... IV

List of figures .................................................................................................. IV

Introduction to alkali metals ........................................................................... 1

1. Classification of elements ............................................................................. 2

2. Electron Configuration of Alkali metals ..................................................... 3

3. Atomic and Ionic Radii ................................................................................ 4

4. Ionization Enthalpy ...................................................................................... 4

5. Hydration Enthalpy ...................................................................................... 5

6. Physical Properties ....................................................................................... 6

7. Chemical Properties ..................................................................................... 7

8. Application .................................................................................................... 8

9. Summary ..................................................................................................... 10

References ....................................................................................................... 11

III
 List of tables
Table 1: Electronic configuration of group 1 elements ....................................... 3

Tale 2: Radii of alkali metals. N.B. Some values are unknown .......................... 4

Table 3: Variation of the first ionization potential for the Group 1 element…….5

Table 4: Atomic and Physical Properties of the Alkali Metals ............................ 6

List of figures
Figure 1: Classification of elements. .................................................................. 2

Figure 2: Hydration enthalpy of alkali metals ..................................................... 6

IV
Introduction to alkali metals:
The alkali metals [Li, Na, K, Rb, Cs and Fr] are elements with the most
pronounced metal properties of all elements in the periodic table. They all react
with water, the product being hydrogen gas and alkali metal hydroxide. As the
metallic character increases with the increase of atomic number (as is the
general rule in the periodic table) the reaction rate increases on going from Li
to Cs. Thus, the reaction of Li with water is a moderate one; that with Na is
vigorous and the metal/hydrogen sometimes even ignites; K reacts very
vigorously and ignition always occurs; a small piece of Rb produces a real
firework, and correspondingly small piece of Cs produces almost instantaneous
explosion, and often the beaker is shuttered into pieces. Reaction of large pieces
of an alkali metal (any of the metals but lithium) with water eventually ends
with a loud explosion [1],
The melting temperatures of the alkali metals vary regularly: with
increasing atomic number, the temperature decreasing monotonously. The
melting temperatures of the two most common alkali metals are 98 °C (Na) and
63 °C (K). Both metals are therefore in the liquid state at the temperature of
boiling water. Upon reaction with cold water enough heat is produced to melt
the above two metals, so a small ball (Na) or a fire-ball (K)1 is always seen
whenever the experiment is performed [2].
Several trends in properties of the alkali metals occur as the atomic mass
increases. Lithium has a much higher specific heat than the other alkalis;
specific heats decrease upon descending the column. Lithium is the lightest of
the alkalis; density increases going down the column. Electron affinities
decrease as atomic weight increases because the influence of the nuclear charge
on the outermost-or valence-electron lessens due to screening by the core
electrons. All alkali metals react readily with water. However, the reaction with
water becomes more violent as the atomic weight of the alkali increases [3].
The chemistry of the alkali metals is determined primarily by the anions
with which they bond. Differences in behavior are due mostly to variations in
sizes of ions and to different heats of hydration. A large variety of inorganic
compounds have been made with alkali metals, including hydrides, hydroxides,
nitrates, nitrides, oxides, and peroxides, permanganates, phosphates, and
silicates. In addition, a large number of organo-alkali compounds have been
prepared in which, most commonly, sodium or potassium combine with various
hydrocarbons [3].

1
1. Classification of elements:
The elements in the long form of the periodic table have been divided into
four blocks - s, p, d and f-block elements. This classification is based on the
type of the atomic orbital in which the outermost electron is located. The s
orbital can accommodate two electrons, while the three p orbitals can
accommodate a maximum of six electrons. Thus, there are two groups of s-
block elements Groups 1 and 2 whose electronic configurations are represented
as [Noble gas] ns1 and [Noble gas] ns2 respectively. There are six groups of p-
block elements Groups 13 to 18. The s and p-block elements are collectively
called the main - group elements or representative elements. The d and f-block
elements are located between the s and p-block elements [4].
The s-block elements are located on the left of the periodic table and
comprise of highly reactive metals. The p-block elements comprise of both
metals and non-metals. On moving from left to right in the periodic table the
metallic character decreases, while on moving downwards, in a particular
group, it increases. Hence, it is apparent that we come across both non-metals
and metals in p-block elements with metallic character being more apparent in
the heavier members of a group. It is more convenient for us to discuss the s
and p-block elements separately since the elements in these two blocks differ
significantly in their physical and chemical properties [4].

Figure 1: Classification of elements.

2
2. Electron Configuration of Alkali metals:
The ns1 electrical configuration corresponds to alkali metals (Table 1). They
can be found on the periodic table in the first row of elements. There are seven
alkaline elements in the periodic table: Lithium, Sodium, Potassium, Rubidium,
Caesium, and Francium. The half-life of francium, a radioactive element, is
incredibly short. At normal temperatures and pressures, hydrogen is more
typically found as a gas than an alkali metal. Hydrogen can take on qualities or
convert into an alkali metal at extremely high pressure.

Alkali metals have a silvery sheen. They are usually kept in oil or other
similar solutions to prevent them from reacting with air. They are so supple that
even a knife can cut through them with ease. Sodium is the most prevalent
among the alkali metals. The radioactive nature of francium makes it extremely
rare.

Ordered according to their atomic number (number of protons), electrical

configurations, and recurrent chemical properties, the Periodic Table displays
the chemical elements. Elements with comparable properties are grouped
together in the same column for easy comparison. Also depicted are four
rectangular blocks with chemical characteristics that are roughly the same. In
general, the elements are metals on the left and nonmetals on the right within a
single row (period) [5].

Table 1: Electronic configuration of group 1 elements

Element Symbol Atomic number Electronic configuration

Lithium Li 3 1s22s1
Sodium Na 11 1s22s22p63s1
Potassium K 19 1s22s22p63s23p64s1
Rubidium Rb 37 1s22s22p63s23p63d104s24p65s1
Caesium Cs 55 1s22s22p63s23p63d104s24p64d105s25p66s1
Francium Fr 87 1s22s22p63s23p63d104s24p64d104f145s25p65d106s26p67s1

Electron configuration can be summarize in the following points [5]:

 Alkali metals have one electron in their valence shell.

 The electronic configuration is given by ns1. For example, the electronic
configuration of lithium is given by 1ns1 2ns1.
 They tend to lose the outer shell electron to form cations with charge +1
(monovalent ions).

3
  This makes them the most electropositive elements, and due to the same
reason, they are not found in the pure state.
3. Atomic and Ionic Radii:
The alkali metal atoms have the largest sizes in a particular period of the
periodic table. With increase in atomic number, the atom becomes larger. The
monovalent ions (M+) are smaller than the parent atom. The atomic and ionic
radii of alkali metals increase on moving down the group i.e., they increase in
size while going from Li to Cs.
As we mention above Atomic and ionic radii of Group IA atoms are the largest
in their horizontal periods in the periodic table. When the outermost electron is
removed to give a positive ion, the size decreases considerably. There are two
reasons for this
a) The outermost shell of electron has been completely removed.
b) The positive charge on the nucleus is now acting on lesser number of
electrons, Le.. attraction increases which brings contraction in size.
Atomic as well as ionic size increases from Li to Fr due to the presence of
one extra shell of electrons [6].
Tale 2: Radii of alkali metals. N.B. Some values are unknown.
Element Atomic radius Ionic radius Covalent radius Van der Waals radius
(Å) (Å) (Å) (Å)
Li 1.52 0.68 1.52 1.82
Na 1.86 0.97 1.53 2.27
K 2.31 1.33 1.90 2.75
Rb 2.44 1.47 2.47 -
Cs 2.62 1.67 2.65 -
Fr - 1.80 2.70 -

4. Ionization Enthalpy:
The ionization enthalpies of the alkali metals are considerably low and
decrease down the group from Li to Cs. This is because the effect of increasing
size outweighs the increasing nuclear charge, and the outermost electron is very
well screened from the nuclear charge.
A quantitative measure of the tendency of an element to lose electron is given
by its Ionization Enthalpy. It represents the energy required to remove an
electron from an isolated gaseous atom (X) in its ground state. In other words,

4
 the first ionization enthalpy for an element X is the enthalpy change (∆ iH) for
the reaction depicted in equation (1).
X(g) → X+(g) + e– (1)
The ionization enthalpy is expressed in units of kJ/mol. We can define the
second ionization enthalpy as the energy required to remove the second most
loosely bound electron; it is the energy required to carry out the reaction shown
in equation (2) [7].
X+(g) → X2+(g) + e– (2)

Table 3: Variation of the first ionization potential for the Group 1 elements.
Element Ionization energy (kJ/mol)
Li 526

Na 502
K 425

Rb 409

Cs 382

5. Hydration Enthalpy:
Hydration enthalpy refers to the energy generated when new interactions
between ions and solvent molecules form. Lithium salts are more soluble than
the salts of other metals of group 1. eg. LiClO 4 is up to 12 times more soluble
than NaClO4. KClO4, RbClO4 and CsClO4 have solubility only 10-3 times of
that of LiClO4 . The high solubility of Li salts is due to strong solvation of small
size of Li+ ion.
Hydration enthalpy of alkali metals are:
a. In the periodic table, hydration enthalpy decreases from top to bottom as
the ionic size of the cation molecules increases.
b. The highly charged ions have a high enthalpy of hydration because they
have more cations. For example, Magnesium has a high enthalpy as
compared to Sodium.
c. The hydration enthalpies of alkali metal ions decrease with increase in
ionic sizes (Li+> Na+ > K+ > Rb+ > Cs+)
d. Li+ has maximum degree of hydration and for this reason lithium salts
are mostly hydrated, e.g., LiCl· 2H2O [8].

5
 Figure 2: Hydration enthalpy of alkali metals
6. Physical Properties:
All the alkali metals are silvery white, soft and light metals. Because of the
large size, these elements have low density, which increases down the group
from Li to Cs. However, potassium is lighter than sodium. The melting and
boiling points of the alkali metals are low indicating weak metallic bonding due
to the presence of only a single valence electron in them. The alkali metals and
their salts impart characteristic color to an oxidizing flame. This is because the
heat from the flame excites the outermost orbital electron to a higher energy
level. When the excited electron comes back to the ground state, there is
emission of radiation in the visible region of the spectrum.
Alkali metals can therefore, be detected by the respective flame tests and can
be determined by flame photometry or atomic absorption spectroscopy. These
elements when irradiated with light, the light energy absorbed may be sufficient
to make an atom lose electron [9].
Table 4: Atomic and Physical Properties of the Alkali Metals
Property Li Na K Rb Cs Fr

Atomic number 3 11 19 37 55 87
–1
Atomic mass (g mol ) 6.94 22.99 39.10 85.47 132.91 (223)
1 1 1 1 1
Electronic configuration [He] 2s [Ne] 3s [Ar] 4s [Kr] 5s [Xe] 6s [Rn] 7s1
Ionization enthalpy / kJ mol –1 520 496 419 403 376 ~375
–1
Hydration enthalpy/kJ mol –506 –406 –330 –310 –276 –
Metallic radius / pm 152 186 227 248 265 –
+
Ionic radius M / pm 76 102 138 152 167 (180)
Melting point / K 454 371 336 312 302 –
Boiling point / K 1615 1156 1032 961 944 –
Density / g cm–3 0.53 0.97 0.86 1.53 1.90 –
⊖ +
Standard potentials E / V for (M /M) –3.04 –2.714 –2.925 –2.930 –2.927 –
Occurrence in lithosphere† 18* 2.27** 1.84** 78-12* 2-6* ~ 10–18 *

6
7. Chemical Properties:
Alkali metals exhibit high chemical reactivity. The reactivity of alkali
metals increases from Li to Cs, since the ionization energy decreases down
the group. All alkali metals are highly reactive towards the more
electronegative elements such as oxygen and halogens. Some characteristic
chemical properties of alkali metals are described blow [10].
I. Reaction with oxygen
All the alkali metals on exposure to air or oxygen burn vigorously,
forming oxides on their surface. Lithium forms only monoxide, sodium
forms the monoxide and peroxide and the other elements form monoxide,
peroxide, and superoxides. These oxides are basic in nature.
4 Li + O2 2Li2O (simple oxide)
2 Na + O2 Na2O2 (peroxide)
M+O2 MO2
(M= K, Rb, Cs; MO2 -superoxide)
II. Reaction with hydrogen
All alkali metals react with hydrogen at about 673 K (lithium at 1073 K)
to form the corresponding ionic hydrides. Reactivity of alkali metals with
hydrogen decreases from Li to Cs.
2M + H2 2 M+H-
(M = Li, Na, K, Rb, Cs)
The ionic character of the hydrides increases from Li to Cs and their
stability decreases. The hydrides behave as strong reducing agents and their
reducing nature increases down the group.
III. Reaction with halogen
Alkali metals combine readily with halogens to form ionic halides MX.
Reactivity of alkali metals with halogens increases down the group because
of corresponding decrease in ionization enthalpy.
2M + X2 2 MX
(M= Li, Na, K, Rb, Cs) (X= F, Cl, Br, I)
All metal halides are ionic crystals. However, Lithium iodide shows
covalent character, as it is the smallest cation that exerts high polarizing
power on the iodide anion. Additionally, the iodide ion being the largest can
be polarized to a greater extent by Li+ ion.
IV. Reaction with liquid ammonia
Alkali metals dissolve in liquid ammonia to give deep blue solutions that
are conducting in nature. The conductivity is similar to that of pure metals

7
 (The specific conductivity of Hg is 104 Ω-1 and for sodium in liquid
ammonia is 0.5 x 104 Ω-1). This happens because the alkali metal atom
readily loses its valence electron in ammonia solution. Both the cation and
the electron are ammoniated to give ammoniated cation and ammoniated
electron.
M + (x + y)NH3 [M(NH3)x ]+ + [e(NH3)y ]-
The blue color of the solution is due to the ammoniated electron, which
absorbs energy in the visible region of light and thus imparts blue color to
the solution. The solutions are paramagnetic and on standing slowly liberate
hydrogen resulting in the formation of an amide.
M+ + e- + NH3 MNH2+ ½H2
In concentrated solution, the blue color changes to bronze color and
become diamagnetic.
V. Reaction with water
Alkali metals react with water to give corresponding hydroxides with the
liberation of hydrogen.
2 Li + 2 H2O 2 LiOH+ H2
They also react with alcohol, and alkynes, which contain active hydrogens.
2 Na + 2 C2H5OH 2 C2H5ONa + H2
H-C ≡ C-H Na H-C ≡ C-Na
Na

Na-C ≡ C-Na
VI. Reducing activity
Alkali metals can lose their valence electron readily hence, they act as
good reducing agents.
M (s) M+(g) + e–
VII. Reaction with carbon
Lithium directly reacts with carbon to form the ionic compound, lithium
carbide. Other metals do not react with carbon directly. However, when they
are treated with compounds like acetylene they form acetelydes [10].
2 Li + 2C Li2C2

8. Application:
 Lithium metal is used to make useful alloys. For example with lead, it
is used to make ‘white metal’ bearings for motor engines, with
aluminum to make aircraft parts, and with magnesium to make armor
plates. It is used in thermonuclear reactions.

8
 Lithium is also used to make electrochemical cells, also used in heat
resistive ceramics and glasses.
 Lithium carbonate is used in medicines.
 Lithium salts are used as mood stabilizing drug.
 Sodium is used to make Na/Pb alloy needed to make Pb(Et)4 and
Pb(Me)4. These organ lead compounds were earlier used as anti-knock
additives to petrol, but nowadays lead-free petrol in use.
 Sodium salts of fatty acids are used in soap.
 Sodium compounds are used in paper, textile, and chemical industries.
 Liquid sodium metal is used as a coolant in fast breeder nuclear
reactors. Potassium has a vital role in biological systems.
 Potassium nitrate is used as a food preservative.
 Potassium chloride is used as a fertilizer. Potassium hydroxide is used
in the manufacture of soft soap. It is also used as an excellent absorbent
of carbon dioxide.
 Caesium is used in devising photoelectric cells [11].

9
9. Summary:
The elements belonging to groups 1 of the modern periodic table are called
s-block elements. They are called so because the valence electron occupies the
s orbitals. The group 1 elements have a general outer electronic configuration
ns1 and are called alkali metals.
Elements belonging to group 1 are highly reactive and forms M +, their
physical and chemical properties show a regular trend as we move down the
group. The atomic and ionic radii increase as we move down the group while
their ionization enthalpies decrease.
They are soft and silvery white in color with low melting points. They are
highly reactive. The compounds of alkali metals are predominantly ionic. They
form metal hydrides and halides with hydrogen and halogens. Their oxides and
hydroxides are soluble in water forming strong alkalis. Important compounds
of sodium include sodium carbonate, sodium chloride, sodium hydroxide and
sodium hydrogen carbonate.
Monovalent sodium and potassium ions are found in large proportions in
biological fluids. These ions perform important biological functions such as
maintenance of ion balance and nerve impulse conduction.

10
References:
[1] Bain, G., Bruce, K., Jacobsen, J. J., Moore, J. W., Chemistry comes alive, Vol. 4, JCE,
http://jchemed. chem.wisc.edu/jcesoft/cca/CCA4/MAINPT/ Cm Cz_elt/Cs.HTM#Water
accessed October, 2006).
[2] Petruševski, V. M., Najdoski, M. Z., A Safe Way of Performing Some Dangerous
Experiments. I. Construction of a Safety Spoon, The Chemical Educator, 7, 81--83, 2002a
[3] Verhovskii, V. N., Techniques and Methods of Performing Chemistry Experiments in a
College, Vol. 2, Zavod za izdavanje udzbenika SR Srbije, Beograd, p. 552, 1968 (translation
from Russian into Serbian).
[4] Gärtner, S. Spotlight on Alkali Metals: The Structural Chemistry of Alkali Metal
Thallides. Crystals 2020, 10, 1013.
[5] S.-G. Wang, W. H. E. Schwarz, analysis of the electronic configuration of atoms, Angew.
Chem., Int. Ed. 2009, 48, 3404- 3415.
[6] L. C. Pauling, The Nature of the Chemical Bond and the Structure of Molecules and
Crystals. An Introduction to Modern Structural Chemistry. 3rd ed., Cornell University Press,
Ithaca, N.Y, 1960, p. 644pp
[7] Greanwood, N. N., Earnshaw, A., Chemistry of the Elements, 2nd edition, Butterworth-
Heinemann, Oxford, p. 1206, 1998.
[8] Down J.L., Lewis J., Moore B., Wilkinson G. The solubility of alkali metals in ethers.
Journal of the Chemical Society (Resumed), 209, 3767, 1959
[9] Atkins, P. W., Physical Chemistry, 2nd edition, Oxford University Press, p. 298 --301,
1982.
[10] Dye J.L., DeBacker M.G., Nicely V.A. Solubilization of alkali metals in tetrahydrofuran
and diethyl ether by use of a cyclic polyether. Journal of the American Chemical Society,
92(17), 5226–5228, 1970.
[11] Dye J.L., Redko M.Y., Huang R.H., Jackson J.E. Role of cation complexants in the
synthesis of alkalides and electrides. Adv. Inorg. Chem., 59, 205–231, 2006.

11