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ESO205A: Nature and Properties of Materials

Assignment 1

Solution with grading guidelines for TAs (Total marks 20)

1. Give the electronic configuration of the fluorine atom and F- ion. Fluorine’s molecular
single bond covalent radius is 0.64 Å and F -radius is 1.17 Å. Explain the difference.

Electronic configuration[1]
F atom: 1s2 2s22p5
F – ion: 1s2 2s22p6

The change in radius could be a combination of the following:


(a) As one more electron is added, we assume that radial distribution of different orbitals
remain the same. However, there will be changes in the degree of attractive force
between electrons and nucleus and also repulsion between electrons. This leads to
increase in the radius of F – ion. [1]

(b) Since the radius is determined from the measurement of equilibrium interatomic
radius, the type of bond will also influence the measured atom/ion radius. F radius is
measured from covalently bonded F2 molecule, whereas F – ion measurement is from
an ionic solid. [1]
2. a) The attractive potential between two ions is WA=-A/r and the repulsive potential
WR=B/rn . Plot the attractive, repulsive and total energy as a function of inter-ionic
distance. Just below this graph, using common inter-ionic distance axis, also plot the
attractive, repulsive and net force, marking the point of equilibrium bond length, as
applicable at 0K.
b) What is the bond length (R) and bond energy (Wo) in terms of A, B and n. Also, the inter
atomic distance is measurable, so sometimes it is useful to write bond energy in terms
of only A and n, along with known R. So do this algebra also.

(a) [2]

(b)

Total interatomic potential,


𝐴 𝐵
𝑊= − +
𝑟 𝑟𝑛
In order to calculate bond length, R, and potential at r=R, i.e
𝑑𝑊
| =0
𝑑𝑟 𝑟=𝑅
or,
𝐴 𝑛𝐵
2
− 𝑛+1 = 0
𝑅 𝑅
Rearranging the above, we obtain
𝑛𝐵
𝑅 𝑛−1 = 𝐴 [1]
𝐵
For discussion: that as ↑, 𝑅 ↑, since n >>1
𝐴

To obtain bond energy corresponding to R,

𝑊0 = 𝑊(𝑅)
1 𝐵
= − [𝐴 − 𝑛−1 ]
𝑅 𝑅
1 𝐵
= − 𝑅 [𝐴 − 𝑛𝐵 𝐴] (substituting for R)

or,
𝐴(𝑛−1)
− 1
𝑛𝐵 𝑛−1
𝐴 𝑛−1 ( )
𝐴
𝑛
𝑊0 = − 𝑅 [ ]= [2]
𝑛

For discussion : as 𝑅 ↑, 𝑊0 ↓.

3. On the basis of the hydrogen bond, explain the anomalous behaviour of water when
it freezes. That is, why is there volume expansion upon solidification?

Water molecule possess a permanent dipole moment because of the difference in


electronegativity of oxygen (3.5) and hydrogen (2.1). There is a net positive charge on
hydrogen and net negative charge on oxygen. Hydrogen bond is formed due to the
attraction between hydrogen-end of one molecule and oxygen-end of the adjacent
molecule. In liquid state, these hydrogen bonds are probably forming and breaking as
molecules move around. [1]

In solid forms, molecules are only vibrating around their positions. Since water is covalently
bonded, hydrogen bonds are directional. In other words, formation of hydrogen bond will
lead to fixed orientation of water molecules with respect to each other in the solid state.
This leads to a relatively open network of water molecules in ice compared to the liquid
state. This is the reason for lower density of ice compared to water. [1]
4.Calculate the Madelung’s constant for a prototype linear NaCl crystal.

Madelung’s constant is the ratio of energy of an ion in a crystal to energy for a pair of
isolated ions.

Fig: Linear crystal of NaCl [1]

For an isolated pair of ions,


𝐴
𝑊0 ∝ − 𝑅 [1]

For a linear crystal,


2 2 2 2
𝑊0 ∝ 𝐴 (− + − + …)
𝑅 2𝑅 3𝑅 4𝑅
Collecting terms by their sign we obtain,
2𝐴 1 1 1 1 1 1
𝑊0 ∝ [− (1 + + + + ⋯ ) + ( + + +. . )]
𝑅 3 5 7 2 4 6
Approximating the two infinite but convergent series, upto five terms leads to
𝐴
𝑊0 ∝ − [−1.79 + 1.02]
𝑅
𝐴
𝑊0 ∝ −1.54 𝑅 [2]

Madelung constant is 1.54

For discussion: Forming a crystal further reduces energy per atom due to large range
interaction.
5. The bonding characteristics of a material is given as W = - A/r + B/rn. Assuming the
equilibrium separation between bonding atoms to be 0.35 nm. Estimate the Young’s
modulus of this material. A = 8.5 X 10-29Jm, n =8.

Given
𝐴 𝐵
𝑊= − +
𝑟 𝑟𝑛
R = 0.35nm; A = 8.5 x 10-29Jm;

n=8

Young’s modulus can be estimated based on interatomic distance, R, as:

𝑠𝑡𝑟𝑒𝑠𝑠 𝑑𝐹 ⁄𝑅 2
𝑌= = |
𝑠𝑡𝑟𝑎𝑖𝑛 𝑑𝑟⁄𝑅 𝑟=𝑅

(We assume here that force F is applied over area R2)


1 𝑑2 𝑊
𝑌=𝑅 | [2]
𝑑𝑟 2 𝑟=𝑅

𝑑2𝑊 2𝐴 𝑛(𝑛 + 1)𝐵


2
| =− 3+
𝑑𝑟 𝑟=𝑅 𝑅 𝑅 𝑛+2

Based on Question 2, we know that

𝐴. 𝑅 𝑛−1
𝐵=
𝑛
Substituting B and n:

1 2𝐴 72𝐴𝑅 7
𝑌= (− 3 + )
𝑅 𝑅 8𝑅10
7𝐴
= [2]
𝑅4
7∗8.5∗10−29 7∗85 𝑁 𝐺𝑁
= (3.5∗10−10 )4 = 𝑥1010 = 3.94𝑥1010 𝑚2 = 39.4 𝑚2 [2]
3.54