Patterns of the Periodic Table

In Mendeleev's day no-one could explain why these patterns existed. However, when scientists see patterns in nature like this, they know there must be underlying "rules" or "laws of nature" causing and controlling the patterns. Perhaps Mendeleev's great contribution was not just the Periodic Table itself, but the stimulus it gave other scientists to investigate the reasons behind the patterns. Within 40 years Science had unravelled the secrets of atomic structure, the electron energy levels, and more. At this sta e our task is to learn some of the atterns.

Melting Point You learned in topic 1 how melting point is determined by the bonding within a substance. Electrical Conductivity As you go across any row ("period") of the table, you will move through a number of metals, then one or two semimetals, then into the non-metals. Therefore, the conductivity will start out high, but rapidly decrease as you encounter a semi-metal, and become extremely low at the non-metals.
r!
, I

At the left side of the table are the very active metals of d1e Activity Series. They are also usually soft, and have relatively low (for metals) melting points. Moving to the right across a period you enter d1e "Transition Block" containing typical hard, high melting point metals, held strongly together by "metallic bonding". Further right you hit d1e Semi-Metals. These often have very high melting points because of their covalent lattice structure. Then you enter d1e Non-Metals which have covalent molecular structures and quite low mp's. At the far right column, each period ends with an Inert Gas which are all single-atom molecules, and have d1e lowest mp of each period. This pattern repeats itself along each period.
o o

CLJ
\ I

llj~H~~tJTEI1:1
Boiling Points follow a similar pattern Melting Points to

Sketch

Graph.

Melting

Points of Elements
I I I
I

o
N

G o
o c..
c

Peaks are Transition or Semi-Metals

Metals

~o

o ... c010

Na

Valencies are the same down each group Chemical Bonding, Valency & Reactivity What you've already learnt about the Activity Series, Ionic and Covalent Bonding and Valency will help you make sense of the following: ("" G 8 I G roup nert ases No chemical reactions, no bonding

Activity

of Non-Metals

Most active at top-right (FIuori ne) Activity (generally) decreases downwards and to the left.

Atomic Radius
The size of an atom is the distance across its outer electron shell. You might think that the atoms along each period would be the same size, because it's the same orbit being added to. However, the increasing amount of positive charge in the nucleus pulls that orbit inwards closer and closer to the centre.

The following diagrams are to scale and show the relative sizes of the first 20 elements

He
The numbers
1

given are the atomic radii in picometres. 12 metre 1 picometre = 1xl 0-

50

Li

0.1 ~I

o
70

0,1
~: 152
01 "I OJ ~I ~I
u

Be

0o o
.~ 1

112

Ne

o o
Si P

o
S
102

o o
Ar

o o O]lO 600 ------------------------------------~

K
231

Na

.~:

MQ

AI

94

Ca
197

Radius decreasing

across a period

o
The Syllabus requires that you produce a table and a graph of the changes in a property across a period, and down a group When you do, you can clearly see how the Periodic Table got its name. "Periodic" means regular intervals". "recurring at This graph shows what a spreadsheet plot gives for the radii of the first 37 elements. otice how the same graphical pattern keeps recurring ... it is a periodic pattern.

Down each group the radius increases. This is because, as you go down a group, you have added an entire electron shell to the outside of the previous layer

Spreadsheet Plot of Atomic Radii aJ ..

...E
Q)

0 0

u
C. .....,
III

0 0
N

::J
"'0

a::
u

ro

0 0

Kr

Ar
He Ne _--------

-----------~ down a
20
gfO

E 0 ...-

------------. Tfend Increasing up

_-----0

Atomic Number
There are a number of irregularities and "glitches" apparent on the graph. It is beyond the scope of this course (and way beyond the K.ISS. Principle) to attempt an explanation of these.

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Ionization Energy
The meaning of tlle "1st Ionization Energy" was explained previously in relation to the Activity Series of Metals.

Successive Ionization Energies

Having added the energy of 1st I.E. and removed an electron from any atom, it is then possible to add more energy and remove a 2nd electron, and a 3rd, and so on. 1st I.E.

+ A (g) where "A" stands for any atom in the gas state

A(g)

----..

+ A (g)

+ + +

2nd I.E.

A+

A+2 (g) A+3

(g)

e
e

Any atom can lose an electron if enough energy is supplied... even atoms which do not normally lose electrons. The Periodic Trend in 1st Ionization Energy

3rd I.E.

A+2

(g)

(g)

You should remember that the very active metals are the ones with low 1st ionization energies. They easily lose their outer electron(s) and so react readily.

...and so on, according to how many electrons the atom has

Once the first electron is removed, tl1e remaining electrons are pulled in tighter to the nucleus. Each one experiences increased force of attraction, so it requires more energy to remove the next electron.

Once the entire outer orbit has been stripped away, the next ionization must remove an electron from an underlying orbit, which requires a huge increase in the next ionization energy. This results in an interesting pattern: Patterns in Successive Ionization Energy Data (values shown are energy measurements) Successive Elements on Period 3 Explanations: 1st I.E. increases to the right because each atom across a period has more and more (+ve) nuclear charge attracting and holding electrons in the orbit concerned. Therefore, it requires more energy to remove an electron. Magnesium 1st I.E. decreases down each group because, at each step down, an extra whole layer of electrons has been added to the outside of tlle atom. The outer shell is further away from the nucleus, and is partially "shielded" from nuclear attraction by the layers of electrons underneath it. Therefore, it becomes easier and easier to remove an electron. Aluminium 2.8.2 2.8.3 0.7 0.6 1.4 1.8 7.7 2.8 10.5 11.6 Element Electron Config. 2.8.1 1st I.E. 0.5 2nd I.E. 4.5 3rd I.E. 6.9 4th I.E. 9.6

Sodium

Notice how the values "jump" (underlined data) as the next ionization has to remove an electron from the next lower orbit. Highest Value
~ot Inert gases

Electronegativity
is a value assigned to each element to describe tlle power of an atom to attract electrons to itself. Atoms with a tendency to gain electrons form negative ions have high values. and ... _..... , '21 ~:
~ 1

Fluorine

included

o .(

I I 1;:::::::::__
J.'
r

._

EI

ectronegatlvlty
of selected

..

V 1

~~ ~~

Atoms with a tendency to lose electrons easily Qow 1st I.E.) and form (+ve) ions have very low values. Once again, there is a pattern in these values in the Periodic Table.

~IL_:..J .. 1r. (values ...1 I ~ ,0.81 ! -0 1 t---,-.-..

I' -----{

~_~-------------t-t- -,r---T-_
Ii :

r ~: ro~)--lr--1----:-- .. ---+-~tr;:;-~-'-l r--r-'-+-,-_+_~-"II--L....JL.J..~L---,-- _.

VlI

0.8

tI-+-l'

decrease to left)

I..-- .. --_..I-_

L__

1.._.. I
!

'--_L-.I

, -" +-+l
elements

a ues r..--.!-.... ~.. "'-"-T-"-'''['-'-''~-''-j

1, rI , I

1~~1~~':~~::~'; ~~Or._j
-1- [3.0! i

-1-

' :1-..-1 .----.1.---1 ~--f' i j, I

I"

-+-~--+l I 2 8\
-1-.-: .. l .._~

i 1+1;:;1--,
!2.5

.1..._J

Atomic Radius ae) across a period because each successive element has af) . (more/less) positive charge in the ag) to attract the electron shell and pull it inwards. As you go As early as 1830, the German a) . noticed patterns in the properties of the elements. In 1860, the English scientist b) proposed a "Law of c) " describing the repeating pattern of properties. It was the Russian d) the e) modern form. He realized that there elements that had not f) so he g) additions. By studying the details of was able to h) properties of the missing elements. who invented , in more or less its were probably many , in his table for later known elements, he very precisely the down a group the radius ah) electron shell is added. as each new

First ai) Energies aj) . across a period, as the increasing amount of nuclear charge makes it more and more difficult to ak) . an electron. The values al) down a group because each extra shell of electrons is am) . (more/less) strongly held than the previous. Successive Ionization Energies measure the energy required to an)............................ another, subsequent electron from an atom. The energy required to remove the next electron is always ao) . (higher/lower). When the next electron happens to be in . the next lower shell, the value ap) by a huge amount. ag) is a value which describes the power of an atom to ar) electrons. The element with the highest value is as) , and values decrease as you move to the at) . and as you move au) the Periodic Table.

Sure enough when discovered, the missing elements were found to have properties i) .

Conductivity, which generally j) the right, as you go from metals to k) and .

to .

Melting Points: tend to l) to about the middle of each period, then m)............................. The highest value is usually a n) metal or elements. The one of the 0) lowest value on each period is always the p)................................ gas member on the extreme g) (right/left) Valencies are r) down each vertical group. Bonding follows the pattern of the main categories of elements. s) form t) bonds when they lose electrons and become u) ions. The Semi-metal elements form only v) bonds. The Non-metals can bond w) or can x) l0ns. Chemical Reactivity electrons to form y)

1. a) Write equations to represent ionisations for a calcium atom.

the 1st, 2nd, 3rd & 4th

b) Between which two of these successive ionisations would you expect a huge increase in the required energy? 2. On each of the following Periodic Table diagrams label the arrows with the word "increasing" or "decreasing" to correctly describe the trend in the direction shown.
r;

.
. . . .

a) Atomic Radius

I (rig ht) I}-t-~ - - - - - - - -

;o""P),

;;) (d?~J~:HffillE!

is different

for metals and non-

metals. The most active metals are located at the left z)................................... (top/bottom) of the table. Generally, activity decreases aa) and to tile ab) The Inert Gases show no chemical activity. Apart from them, the most active non-metals are located on the right ac) (top/bottom) of the table. Activity generally decreases as you move ad) and . WHEN COMPLETED, BECOME SECTION WORKSHEETS SUMMARIES

b) Electronegativity Also indicate ("H"&"L") the position of elements with highest & lowest values.

Quantities in Chemical Calculations

Atoms, molecules and ions always react with each other in fixed, whole-number ratios. That's why balancing an equation is so important... it actually brings the equation into line with what is happening at the particle level. For example, when hydrogen and oxygen react to form water, the balanced equation is

Defining the Mole

For technical reasons, the "atomic standard" used to compare the masses of all atoms is the carbon atom, which contains 6 protons 6 neutrons 6 electrons

This is a true description molecules:

of what is happening

to the

en
CD

m
Since this is the standard definition of the mole is:
2 Molecules

of

comparison,

the formal in

of H20

"the number of atoms contained exactly 12 grams of carbon-12"

However, when we carry out chemical reactions in the laboratory or in Chemical Industry, we cannot see or count the molecules. Instead, we measure the mass or volume of substances. To measure out the correct numbers of particles for a reaction we need a simple way to convert masses and volumes to numbers of molecules, and vice-versa. That's the purpose of

Note:

In Topic 1 it was pointed

out that the Mass

Number for any atom is a whole number. It has still not been explained why the ''Atomic Weights" in the Periodic Table are mostly not whole numbers. This WILL be explained in a later topic. If you cannot wait, go find out about "Isotopes".

The Mole
1 mole of any element or compound same number of particles. contains exactly the 1 mole of each substance has a different mass, because the atoms and molecules all weigh differently. The really clever and convenient thing about the mole is its link to the Periodic Table and the "Atomic Weights" shown.

Avogadro's Number
Just how many atoms are in 1 mole? Obviously, it is a very large number. We now know that it is about 6,000 billion trillion. Avogadro's Number

6.022
particles

X in 1 mole of anything

1023

6
Carbon

18

82

This number is named in honour who you will learn about soon. 207.2 grams of Lead , contains .; ,. 6.022 x 1023 ,. Lead atoms

of an Italian scientist

C
I

At Argon
39.95
',=
,
HAS

Ph Lead
207.2

39.95 grams of Argon

..J

1~'(~1 =
1 " mo e, 12.01 grams' 1

l...~ . .,...,.

6.~~~t:i~;23 Argon atoms

_~~".

1 mole.... 39.95 grams""

1 mole,. 207.2 grams

_--_...
........

.;

,.

12.01grams of C b ar on contains "'" 6.022 x 1023 Carbon atoms

EACH OF THESE

H~ SAME NUMBER

...

OF ATOMS

"

. ".........

_-_

16

..... - ....

~----

.,. .. "Copyright

~' e

". ".

2005-2006

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Calculating Mole Quantities

You need to be able to calculate mole quantities in terms of both mass and number of particles. Molar Mass The "Molar Mass" of any chemical species is the mass (in grams) of 1 mole of the substance. You need to add up all the Atomic Weights of all the atoms given in the formula. Examples: Name Argon Sodium Formula Ar Molar Mass (g) 39.95 22.99

Moles and Numbers

of Particles
contains Avogadro's

Since one mole of any substance Number of particles: No. of moles

= No.

of particles you have Avogadro's Number

Example Calculations 1. How many moles are present 24 containing 7.88 x 10 atoms? in a sample of lead

Na

Oxygen CWorine

(16.00 x 2) (35.45 x 2)

32.00 70.90

7.88xl0 ---23 6.022xlO = 13.1 mol

24

2. a) How many atoms of lead are needed to make 0.0250 mole? b) What would be the mass of this quantity? Solution

Water Carbon Dioxide Sodium chloride

H20 CO2 NaCl

(1.008x2

+ 16.00)

(12.01 + (16.00x2) (22.99 + 35.45)

18.016 44.01 58.44

a)n=~

NA

so

= n x NA =

= 1.51 x 1022 atoms

0.0250 x 6.022x10

23

b) m

n x M1vl

0.0250 x 207.2 (molar mass of Pb)

= 5.18 g Number of Moles in a Given Mass

When you weigh a chemical sample you then need to be able to calculate how many moles this contains.

Mole Quantities in Chemical Equations

No. of moles

= mass
m

of substance molar mass

vou have

When you consider an equation like

n=

MM

CD
Example Calculations a) 5.23g of magnesium? b) 96.7g of water? 1. How many moles in

C()

m
2 Molecules

of H20

a)

n = --ill..-

MM
MM

5.23 24.31

= 0.215 mol
However, the number of molecules reacting is really just a ratio. The actual numbers might be

b)

n = --ill..-

= =

_96_.7 _ (2x1.008 + 16.00) 96.7/18.016 5.37 mol

2. What mass is needed if you want to have 1.50 moles of salt (sodium cWoride)?
n

= --ill..M:M

so m

= n x MM = -1.50 x (22.99 + 35.45)

= 1.50 x 58.44 = 87.7 g

or, (let's use Avagadro's number) + NA 02 --.(2 x NA) H2

(2 x NA) H20

The Balancing Coefficients May be Interpreted

in a Chemical Equation as Mole Ratios

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Mole Quantities in Chemical Equations

Calculating Mass Quantities in Reactions

(cont.) be Mole calculations allow you to calculate the mass products and reactants involved in a reaction. Example Problem Aluminium burns to form aluminium oxide. If 4.29g of aluminium was burned, a) what mass of oxygen would be consumed? b) what mass of aluminium oxide would be formed? Solution Always start with the balanced equation: of

The balancing coefficients of an equation can interpreted as the mole ratio of reactants and products.

means or, or,

2 mol. reacts with 1 mol. to form 2 mol. 4 mol. reacts with 2 mol. to form 4 mol. 100 mol. reacts with 50 mol. to form 100 mol. quantities.

or any other proportional

Example Problem a) If 0.50 mol of sodium reacted completely with hydrochloric acid, how many moles of products would be formed?

4Al
mole ratio

,
4

+ 30z
3 n = ---1!L MM = 4.29 26.98 = -,.0.159 mol
".'" '"

No. of moles of Aluminium:

Solution a) The balanced

equation

is

a) Mass 02 consumed: mole ratio Al : 02 = 4: 3 ~,,/ :. moles of 02 = 0.159 x...l.. :. mass of 02: m

,/"

--

'\.

,
\ "

= 0.119 mol

mole ratio

4 n x MM = 0.119 x 32.00
= 3.81 g

~ ; ,

Answer: 0.25 mol of Hz and 0.5 mol of NaCl b) Mass of Hydrogen: Mass of salt: m = n x MM = 0.25 x 2.016 = 0.50 g m = n x M,.\1 = 0.50 x 58.44

b) Mass AI203 produced: mole ratio Al : AI203 :. moles of Alz03 = :. mass of A1203: m

4: 2 (i.e. l/Z x 0.159

~J//

,,

, ,

"

= 0.0795 mol

= 29 g

= n x MM

= 0.0795 x 101.96 = 8.11 g

Practical Work: Using Mass & Mole Ratios to Determine

a Formula

A common experiment is to burn a piece of magnesium in a crucible, as suggested by dle diagram. The difficulty is to open the lid enough to admit oxygen for complete combustion, but to limit ilie loss of powdery product.

Careful measurement of mass allows the empirical formula for magnesium oxide to be determined. Analysis of Results Remember that to convert any mass to moles: n=m/MM Mass of empty crucible 42.74 g Mass of magnesium 2.05 g Mass of crucible Elements Magnesium + product after burning Ratio of masses: 2.05 g Ratio of moles: 2.05/24.31 :. Mass of magnesium oxide 0.0843 mol formed = 3.48 g 0.0843/0.0669 :. Mass of oxygen in 1.26 compound 1.07 g Nearest whole number ratio 1 :. Empirical Formula is MgO

Oxygen 1.07 g 1.07 / 16.00 0.0669 mol : 0.0669/0.0669 1 1

(divide by Atomic Weight)

(divide boili by the smaller) ,

: There is often a large error ~due to incomplete burning

.................................................

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Comparing Mass Changes When Metals Burn

Atoms always react in simple whole-number mole ratios, but atoms have different masses, and compounds have various formulas, so the result is that chemicals do NOT react in simple ratios by mass. That's why we need the mole ... we measure quantities by their mass, but this makes no sense until moles are calculated. The syllabus requires that you should consider the mass changes involved when various' metals combine with oxygen to form their oxide compound. The following table shows the mass changes for ;lOOg of the metal in each case: 100g of Metal Lithium Iron Zinc Lead Formula of oxide Liz FeZ03 ZnO PbOz Mass 0z needed(g) 115 43 49 15 Mass of Oxide formed 215 143 149 115

A Little History ... How the Mole was Invented

The "mole" as a measure mathematically convenient chemical calculations. of chemical quantities, is a device (a "trick") to help

Gay-Lussac's

Law

Joseph Gay-Lussac was a French scientist with an unfortunate name, by modern standards. He lived 200 years ago, and was very interested in flight using balloons, so he investigated the way gases react chemically. After a series of clever experiments, in which the volumes of reacting gases were measured, in 1808 he proposed the "Law of Combining Volumes": When measured at constant temperature and pressure, the volumes of gases in a chemical reaction show simple, whole-number ratios to each other. The volume of a gas is easily changed by temperature and pressure, so it is very important that the volumes are all measured at the same conditions.

Empirical Formulas v Molecular Formulas

You are reminded that a molecular formula really does describe the atoms present in a molecule. The molecular compound methane, has formula CH4, because that's exactly what each molecule contains ... 1 carbon atom and 4 hydrogen atoms. Lattice structures, either ionic or covalent are NOT molecular. Example: sodium chloride, NaCl The formula does NOT describe a molecule, but only gives the simplest ratio between the bonded atoms ... this is an empirical formula. On the previous page was an example of how formulas are determined by analysing the mass composition of a compound. You should note that this method can only produce an empirical formula. (In fact, the word "empirical" means something determined by experiment, not by theory.) If a molecular compound, with molecular formula XzY6 was analysed by mass measurements, its empirical formula would be calculated to be :>"''Y3 ... simplest ratio of atoms. The mole ratios are the discovered by Gay-Lussac! same as the volume ratios Hydrogen(g) 1 litre H ydrogen(g) 2 litres Hydrogen(g) 3 litres

+ Chlorine(g)~
1 litre

Hydrogen chloride(g) 2 litres . Water(g) 2 litres (vapour)

+ Oxygen(g)
1 litre

+ Nitrogen(g)
1 litre

--..

Ammonia(g) 2 litres

Notice that in every case, that the volumes are always in a simple, whole number ratio to each other. Now consider the balanced example reactions: equations for these three

enter .Avogadro!

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Avogadro's Hypothesis
The Italian, Amadeo Avogadro (1776-1856) was trained in Law, but became very interested in Science. In 1811, he noticed the similarity between Gay-Lussac's Law (an empirical "law" based on experiment) and the concept that atoms must combine in simple, whole number ratios to form compounds.

Molar Volume of a Gas

If 1 mole of any chemical species contains the same number of particles (Avogadro's Number) AND if equal volumes of gases contain equal number of particles (Avogadro'S Hypothesis), then it follows that 1 mole of any gas must occupy the same volume, if measured at the same temperature and pressure. This volume is the "Molar Volume" and is the same for every gas. It is measured at the standard set of conditions known as Standard Laboratory Conditions (SLC); 25C and 1 standard atmosphere of pressure.

Equal Volumes of all Gases Contain Equal Numbers of Molecules (when measured at the same conditions of temperature and pressure)

Mole Calculations Involving Gases

This additional knowledge opens up the opportunity to carry out quantity calculations which involve mass and volumes of gases. Example Problems

1.
Prior to Avogadro, it was assumed that the the reaction involved single atoms, like this: If 15.65g of calcium carbonate (CaC03) was completely decomposed by heat, what volume of carbon dioxide gas would be produced (if measured at SLC)? Solution Always begin with the balanced equation for the reaction. CaC03(s) mole ratio = 1 Chlorine(g) ~ 1 volume Hydrogen chloride(g) 2 volumes Moles of CaC03: . : CO2(g) 1

+
: 15.65 100,09

Hydrogen{g) 1 volume

+
:

CaO(s) 1

n =..J.!L = j\1},,f

= 0.1564 mol

Mole ratio is 1 : 1, so moles of CO2 formed = 0.1564 Now, reasoned Avogadro, gases react in simple, wholenumber volume ratios because each litre of gas has the same number of molecules in it. Therefore, to get the volume ratios shown above, each hydrogen molecule, and each chlorine molecule, must have 2 atoms! i.e. Hydrogen is H2(g) and Chlorine is Cl2(g)' and the correct equation is :. Volume of CO2 = 0.1564 x 24.8...... 3.88 L (at SLC)

Molar Vol. of all gases at SLC

2.
What volume of hydrogen gas (at SLC) would be produced if 10.00g of lithium metal was reacted with sulfuric acid? Solution 2 Li(s)

+
:

Then, for the same reaction, scientists could measure the masses of these gases as well as volumes. This showed that chlorine atoms must be about 35 times heavier than hydrogen ... chemists were on the way to figuring out the relative atomic weights of elements, and being able to calculate chemical quantities. Although he did not invent the concept of the mole, we name the number of particles in 1 mole in Avogadro's honour ...

. H2(g) 1

+ Li2SO 4(aq)
1

Moles of lithium: n = ..J.!L = 10.00 = 1.441 mol MM 6.941 Mole ratio is 2:1, so moles of H2 = 1/2 X 1.441=0.7204 :. Volume of Hz = 0.7204 x 24.8

= 17.9 L (at SLC)