principles of chemistry i chem 1211 chapter 8 dr. augustine ofori agyeman assistant professor of...
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PRINCIPLES OF CHEMISTRY I
CHEM 1211
CHAPTER 8
DR. AUGUSTINE OFORI AGYEMANAssistant professor of chemistryDepartment of natural sciences
Clayton state university
CHAPTER 8
PERIODIC PROPERTIES OF
THE ELEMENTS
- Elements in a given group have similar chemical propertiesbecause the outer-shell electron arrangements are similar
Group IIA elementsBe: 1s22s2
Mg: 1s22s22p63s2
Ca: 1s22s22p63s23p64s2
Sr: 1s22s22p63s23p64s23d104p65s2
CLASSIFICATION OF THE ELEMENTS
- The last electron in an element’s electron configuration causes the difference in the electron configuration of the
preceding element and is referred to as the distinguishing electron
HomeworkWrite notes (one page) on the different classifications of the elements based on electronic properties. Briefly describe the
s-area, p-area, d-area, and the f-area.
CLASSIFICATION OF THE ELEMENTS
CLASSIFICATION OF THE ELEMENTS
Elements can be classified as Metals or Nonmetals
- Based on physical properties
Elements can also be classified as Noble-gas, Representative,
Transition, or Inner Transition- Based on electron configuration
CLASSIFICATION OF THE ELEMENTS
Noble-gas Elements
- Group VIIIA (18) elements on the periodic table (far right column)
- Gases at room temperature
- Little tendency to form chemical compounds
- Electron configuration ends in p6
- Completes p subshell (except Helium)
- Nonmetals
CLASSIFICATION OF THE ELEMENTS
Representative Elements
- Elements in the
s-area (Groups IA and IIA)
first five columns of the p-area (Groups IIIA, IVA, VA, VIA, and VIIA)
- Metals and nonmetals
CLASSIFICATION OF THE ELEMENTS
Transition Elements
- Elements in the d-area of the periodic table
- Groups IIIB (3), IVB (4), VB (5), VIB (6), VIIB (7), VIIIB (8, 9, 10), IB (11), and IIB (12)
- Distinguishing electron in a d subshell
- Metals
CLASSIFICATION OF THE ELEMENTS
Inner Transition Elements
- Elements in the f-area of the periodic table
- The two-row block of elements below the main table
- Distinguishing electron in an f subshell
- Metals
VALENCE ELECTRONS
- Electrons in the highest principal quantum number of an atom, and any electrons in an unfilled subshell
from a lower shell
- Electrons in filled subshells that have lower principal quantum numbers
CORE ELECTRONS
VALENCE ELECTRONS
- Representative elements in the same group of the periodic table have the same number of valence electrons
- The number of valence electrons for representative elements is the same as the group number (with A) in the periodic table
- The maximum number of valence electrons for any given element is eight
VALENCE ELECTRONS
- Not all electrons in a given atom participate in bonding
- Only valence electrons are available for bonding
- For representative and noble-gas elements these electrons are always found in the s or p subshells
VALENCE ELECTRONS
- The electron configuration can be used to determine the number of valence electrons of an atom
C: 1s22s22p2
O: 1s22s22p4
Na: 1s22s22p63s1
As: 1s22s22p63s23p64s23d104p3
ELECTRON CONFIGURATION OF IONS
Cl: [Ne]3s23p5
Cl-: [Ne]3s23p6
Na: [Ne]3s1
Na+: [Ne]
F : 1s22s22p5
F- : 1s22s22p6
Co: [Ar]3d74s2
Co3+: [Ar]3d6
EFFECTIVE NECLEAR CHARGE
-Negatively charged electrons are attracted to the positively charged nucleus
The force of attraction between an electron and the nucleus- Depends on the magnitude of the net nuclear charge acting
on the electrons
- Depends on the average distance between the nucleus and the electron
(Coulombs law)
The force of attraction- Increases with increasing nuclear charge
- Decreases with increasing average distance between electrons and the nucleus
- Electrons also experience repulsion by other electrons in the atom
Zeff = Z – S
Zeff = effective nuclear charge Z = actual nuclear charge (number of protons in the nucleus)(> Zeff)
S = screening constant (represents number of core electrons)
EFFECTIVE NECLEAR CHARGE
Atomic number of Na = 11Number of valence electrons = 1Number of core electrons = 10
As simplified from this modelZ = 11S = 10
Zeff = 11-10 = +1
In actual factZeff in Na is about +2.5
EFFECTIVE NECLEAR CHARGE
In general Zeff in s orbital > Zeff in p orbital > Zeff in d orbital > Zeff in f orbital
- This is the result of the trend in energy levels ns < np < nd < df
- Zeff increases across the periods (from left to right) in the periodic table (Z increases but S remains the same)
- Zeff changes slightly down the groups in the periodic table(essentially the same in a given group)
EFFECTIVE NECLEAR CHARGE
SIZES OF ATOMS
- Atomic radius tends to decrease across the periods (from left to right) in the periodic table
- Due to increase in effective nuclear charge which draws valence electrons closer to the nucleus
- Atomic radius tends to increase down the groups (from top to bottom) of the periodic table
- Due to increase in principal quantum number of the outer electrons (number of shells)
- Cations are smaller than their parent atoms
- Decrease in the number of electrons decreases electron-electron repulsions
- Anions are larger than their parent atoms
- Increase in the number of electrons increases electron-electron repulsions
- Ionic size increases down the group of the periodic table for ions carrying the same charge
SIZES OF ATOMS
ISOELECTRONIC SERIES
- A group of atoms and ions containing the same number of electrons
Due to the same number of electrons- Ionic radius decreases with increasing nuclear charge (electrons are more strongly attracted to the nucleus)
increasing nuclear charge O2- , F- , Na+ , Mg2+ , Al3+
S2- , Cl- , K+ , Ca2+ , Ga3+
Se2- , Br- , Rb+ , Sr2+ , In3+
decreasing ionic radius
IONIZATION ENERGY
- The energy required to remove an electron from a gaseous atom or ion
X(g) → X+(g) + e-
E is positive
- The atom or ion is assumed to be in its ground state
- The highest energy electron is always removed first
Units: kJ/mol96.485 kJ/mol = 1 eV
Ionization Energies of Magnesium (Mg)
Mg(g) → Mg+(g) + e- I1 = 738 kJ/mol
Mg+(g) → Mg2+(g) + e- I2 = 1450 kJ/mol
Mg2+(g) → Mg3+(g) + e- I3 = 7734 kJ/mol
I1 < I2 < I3
IONIZATION ENERGY
First Ionization Energy (I1)- Energy required to remove the highest energy electron of an atom
- The first electron is removed from a neutral atom
- The second electron is removed from a positive ion (more difficult)
- Increase in positive charge binds electrons more tightly
- Large jump is observed in going from removal of valence electrons to removal of core electrons
IONIZATION ENERGY
- First ionization energy increases across the period of the periodic table (from left to right)
- Electrons added in the same principal quantum number do not completely shield increasing nuclear charge
- First ionization energy decreases down the group of the periodic table (from top to down)
- As n increases, the size of orbital increases (distance from nucleus increases) and electrons are easier to remove
IONIZATION ENERGY
- Discontinuities are due to electron repulsions and shielding (Be to B, N to O)
- Representative elements show a larger range of values of I1 than the transition-metal elements
- Smaller atoms have higher ionization energies
IONIZATION ENERGY
- Several cations with the pseudo-noble-gas electron configurationare more stable
[noble gas](n-1)d10
In: [Kr]5s24d105p1
In+: [Kr]5s24d10
Pseudo = In3+: [Kr]4d10
Sn: [Kr]5s24d105p2
Sn2+: [Kr]5s24d10
Pseudo = Sn4+: [Kr]4d10
PSEUDO-NOBLE-GAS CONFIGURATION
ELECTRON AFFINITY
- The energy change that occurs when an electron is added to a gaseous atom
- A measure of the attraction of the atom for the added electron
- Energy is released when an electron is added to most atoms
X(g) + e- → X-(g)
E is negative
Units: kJ/mol
Cl(g) + e- → Cl-(g) E = -349 kJ/mol
- The greater the attraction between an atom and an added electron the more negative the atom’s electron affinity
- Electron affinities for noble gases are positive values (E > 0)
- Halogens have the most negative electron affinities
- Electron affinity changes slightly down the group of the periodic table
ELECTRON AFFINITY
METALS
- Refer to chapter 2 for properties of metals
- Metals tend to have low ionization energies
- Metals form positive ions relatively easily
- Metals lose electrons (oxidize) when they undergo chemical reactions
Charge on metals- Alkali metals: 1+
- Alkaline earth metals: 2+
METALS
- The charge on transition metals do not follow any obvious pattern
- Transition metals are able to form more than one positive ion
- Compounds of metals and nonmetals are ionic
2Na(s) + Cl2(g) → 2NaCl(s) (contains Na+ and Cl- ions)
Most Metal Oxides are Basic
- Dissolve in water to form metal hydroxides
Na2O(s) + H2O(l) → 2NaOH(aq)
O2-(aq) + H2O(l) → 2OH-(aq)(net ionic equation)
- React with acid to form salt and water
NiO(s) + 2HNO3(aq) → Ni(NO3)2(aq) + H2O(l)
METALS
NONMETALS
- Refer to chapter 2 for properties of nonmetals
- Nonmetals tend to have high electron affinities
- Nonmetals tend to gain electrons when they react with metals
- Compounds composed of only nonmetals are generally molecular substances
Most Nonmetal Oxides are Acidic
CO2(g) + H2O(l) → H2CO3(aq)(acidity of rainwater)
- Dissolve in basic solutions to form salt and water
CO2(g) + 2NaOH(aq) → Na2CO3(aq) + H2O(l)
NONMETALS
ALKALI METALS (GROUP IA)
- Alkali means ‘ashes”
Relatively abundant in the - earth’s crust (Na, K)
- sea water - human bodies
- Have low densities and melting points
- Very reactive and readily lose an electron to form 1+ ions
- Form hydrides with hydrogen and sulfides with sulfur
2M(s) + H2(g) → 2MH(s) 2M(s) + S(s) → M2S(s)
- React vigorously with water to produce hydrogen gas and alkali metal hydroxide
(very exothermic and may explode)
2M(s) + 2H2O(l) → 2MOH(aq) + H2(g)
ALKALI METALS (GROUP 1A)
- Can react with oxygen to form oxides, peroxides, and superoxides
Li forms only oxides (O2-)4Li(s) + O2(g) → 2Li2O(s) (lithium oxide)
Na can form peroxides (O2
2-)2Na(s) + O2(g) → Na2O2(s) (sodium peroxide)
K, Rb, and Cs can form peroxides (O22-) and superoxides (O2
-)K(s) + O2(g) → KO2(s) (potassium superoxide)
ALKALI METALS (GROUP 1A)
ALKALINE EARTH METALS (GROUP 2A)
Compared to alkali metals- harder
- more dense - higher melting points
- less reactive than the respective adjacent alkali metal
- Tend to lose two outer s electrons to from 2+ ions
- Give off characteristic colors when heated in a flame (salts used in fireworks)
- Reactivity increases down the group
- Beryllium does not react with water
- Magnesium reacts slowly with water
- Calcium and elements below react readily with water Ca(s) + 2H2O(l) → Ca(OH)2 + H2(g)
ALKALINE EARTH METALS (GROUP 2A)
HYDROGEN
- First element in the periodic table (1s1 electron configuration)
- Nonmetal
- Can be metallic under extreme pressures
- Colorless diatomic gas
- Has very high ionizaton energy - More than double those of alkali metals
- Due to absence of nuclear shielding of the 1s electron
- Does not easily lose its valence electron
- Share with nonmetals to form molecular compounds
- Can lose its electron to form a cation (H+)
- Can gain electron to form the hydride ion (H-)
HYDROGEN
CHALCOGENS (GROUP 6A)THE OXYGEN GROUP
- Properties change from nonmetallic to metallic down the group Nonmetallic properties: oxygen, sulfur, selenium
Metallic properties: tellurium and below
- Oxygen is a colorless gas at room temperature
- The other group members are solids
- Oxygen exists as O2 (oxygen gas) and O3 (ozone) - Allotropes (different forms of the same element in the same state)
- O2 can produce O3 in lightning storms
3O2(g) → 2O3(g) Ho = 284.6 kJ
- Sulfur also has several allotropic forms - The most common is S8 (yellow solid)
CHALCOGENS (GROUP 6A)THE OXYGEN GROUP
THE HALOGENS (GROUP 7A)
- All halogens are nonmetals
- Melting and boiling points increase with increasing atomic number
- Consist of diatomic molecules (F2, Cl2, Br2, and I2)
- Form colored gases
THE HALOGENS (GROUP 7A)
At room temperature - Fluorine and chlorine are gases
- Bromine is a liquid - Iodine is a solid
- Have highly negative electron affinities
- Tend to gain electrons to form 1- ions
- Reactivity decreases down the group
- React readily with most metals to form ionic halides
- React with hydrogen to form gaseous hydrogen halides H2(g) + X2 → 2HX(g)
- Hydrogen halides dissolve in water to form acids [HCl(aq)]
- Fluorine is very reactive (dangerous)
- Chlorine is the most industrially useful
THE HALOGENS (GROUP 7A)
THE NOBLE GASES (GROUP 8A)
- Nonmetals
- Monatomic
- Gases at room temperature
- Have completely filled s and p subshells
- Have high first ionization energies
- Have stable electron configuration
- Unreactive