Group 17 Elements

Physical and Chemical Properties of Group 17 Elements (Halogens)

The elements that are present in group 17 are fluorine, chlorine, bromine, iodine, and astatine. They are called halogens as they react with metals to give salts.

ELECTRONIC CONFIGURATION

The electronic configuration of the outermost shell of the elements of group 17 is ns2 and np5. Therefore there are 7 electrons in the outermost shell.

There are 7 electrons in the outermost shell of the elements belonging to group 17. The outermost shell is short by one electron to achieve an octet. These elements require one more electron to achieve an octet or ideal gas configuration.

Halogens are the most reactive non-metals. This is due to their tendency to pick up or share an electron to achieve an octet or closest inert gas configuration.

OCCURRENCE

Halogens do not exist in their free state. Halogens exist in all three different states of matter.

Astatine is radioactive in nature and exists in a solid state at room temperature. Fluorine is the 13th richest element by weight in the crust of the world. It exists in the gaseous state in room temperature. It usually exists as insoluble fluorides, cryolites, fluorspar, and fluorapatite. Fluorine is also found in the soil, plants of stream water and bones and teeth of creatures. Chlorine is the 20th richest element found by weight in the Earth's crust. It exists in its gaseous state at room temperature. Water in the ocean comprises of 1.5% by weight of sodium chloride. The dry bed of the ocean contains sodium chloride. Iodine exists as solid at room temperature. Chlorine, bromine, and iodine are present in the ocean water as chlorides, bromides, and iodides. Bromine exists as a liquid at room temperature.

ATOMIC PROPERTIES

The atomic properties of group 17 which are going to be discussed are:

1) Ionic and atomic radii
2) Ionization enthalpy
3) Electron gain enthalpy
4) Electronegativity

TRENDS IN ATOMIC AND IONIC RADII

Atomic radii are the measure of the distance from the center of an atom to the outermost shell containing electrons. Ionic radii are the measure of the size of an atom's ion.

As we go down the group, the atomic and the ionic radii tend to increase as an extra energy shell is added. The reason the elements belonging to this group have smaller atomic radii compared to other elements is because of high atomic charge.

IONIZATION ENTHALPY

The energy required to remove an electron from its valence shell is known as ionization energy. As we move down group 17, the ionization energy decreases. This is because as we move down the group the size of the atom increase which decreases the attraction of the valence electrons and the valence electrons therefore only little ionization energy is required to remove an electron from the valence shell from any halogens. The ionization energy of fluorine is comparatively higher than any other halogen which is due to its small size because of which greater will be the attraction between the core and the valence shell. There higher the ionization energy.

ELECTRON GAIN ENTHALPY


Electron Gain EnthalpyKJ mol-1
F-333
CI-348
Br-324
I-295


The energy released when an electron is added to an isolated gaseous atom is known as electron gain enthalpy. Halogens have negative electron gain enthalpy. However, on moving down the group the electron gain enthalpy turns out to be less negative.

Exception: chlorine has a higher gain of enthalpy when compared to fluorine. This is attributed to the small size of fluorine due to which there is higher inter-electronic repulsion in the small 2p orbitals and lesser attraction for the incoming electron. chlorine has more negative electron pick up enthalpy than fluorine. I.e. among all, chlorine has the most extreme negative electron pick up enthalpy. It is a result of the small size and reduced 2p sub-shell of the fluorine atom. Attributable to the small size of the fluorine particle, the approaching electron encounters a more noteworthy measure of repulsion from the electrons that are now present.

ELECTRONEGATIVITY

The tendency of an atom to attract electron or bonding pair of electrons i known as electronegativity. Halogens have high electronegativity. The electronegativity decreases as we move down group 17 because of the increase in nuclear radii. In group 17, fluorine is the most electronegative element.

PHYSICAL PROPERTIES

The physical properties of elements include:

1) Physical state
2) Color
3) Solubility
4) Metallic character
5) Density
6) Melting and boiling point
7) Bond dissociation energy

  • 1. PHYSICAL STATE

  • Fluorine and chlorine are present in the gaseous state. Bromine is present in the liquid state. Iodine is present in a solid state. All of these elements exist as diatoms.

  • 2. COLOR

  • The elements of group 17 exhibit different colors.
    Fluorine has a pale yellow color. Chlorine has a greenish yellow color. Bromine has a reddish brown color. Iodine has a dark violet color.

  • 3. SOLUBILITY

  • Fluorine and chlorine are soluble in water. Bromine and iodine dissolve in organic solvents.
    HalogenColor in waterOrganic Solvent
    FluorinePer YellowYellow
    ChlorineGreenish YellowGreen
    BromineReddish BrownBrown
    IodineBrownPurple
    Astatine


    HalogenDensity
    Fluorine0.0017
    Chlorine0.0032
    Bromine3.1028
    Iodine4.933
    Astatine


  • 4. METALLIC NATURE

  • As we move down the group the metallic nature of the elements increases. These elements are nonmetallic in nature due to high ionization enthalpy.

  • 5. DENSITY

  • As molecular weight increases down the group, the density decreases.

  • 6. MELTING AND BOILING POINTS

  • As we move down the group, the melting and boiling point increases. This is because as we go down the group the size of the atoms increases, therefore, the vander walls force of attraction also increases.

  • 7. BOND DISSOCIATION ENERGY

  • Bond dissociation energy is the energy required to break the bond into atoms, each with one electron of the original shared pair. The bond dissociation energy decreases as we go down the group except for fluorine. Fluorine has low bond dissociation energy due to its small atomic radius.

  • 8. OXIDATION STATES

  • The general electronic configuration of group 17 is: ns2np5
    All the elements of group 17 have 7 electrons in its valence shell. These elements require one electron to finish their octet. They can complete their octet either by picking up an electron or sharing an electron. The oxidation states of all the elements belonging to this group are -1.

    Except for fluorine, bromine chlorine and iodine have free d-orbital in their valence shells. Due to this, they display different oxidation states like +1, +3, +5, +7 along with -1. These positive oxidation states are oxoacids, interhalogens, and oxides.

    CHEMICAL PROPERTIES

  • 1. OXIDIZING POWER

  • Halogens are great oxidizing agents. Fluorine can oxidize all halide particles to halogen in a solution. However, oxidizing power decreases as we move down the group.
    Chlorine can oxidize bromide to bromine and iodide to iodine.
    Cl2 + 2Br¯ → Br2 + 2Cl¯
    Cl2 + 2I¯ → I2 + 2Cl¯
    Bromine can oxidize iodide to iodine.
    Br2 + 2 I¯ → I + 2Br¯
    Cl2 (aq) Br2 (aq) I2 (aq)
    Cl–(aq)Remains as a yellow solution (no reaction)Remains as a brown solution (no reaction)
    Br–(aq)Yellow solution forms (Br2 forms)Cl2 + 2 Br- → 2 Cl- + Br2Remains as a brown solution (no reaction)
    I–(aq)Brown solution forms (I2 forms)Cl2 + 2 I- → 2 Cl- + I2Brown solution forms (I2 forms)Br2 + 2 I- →2 Br- + I2


    Halide particles can also act as reducing agents. The reducing power decreases as we move down the group.

  • 2. REACTION WITH HYDROGEN

  • Acidic hydrogen halides are formed when halides react with hydrogen. The reactivity of halogen towards halogen decreases as we move down group 17. Therefore, their acidity also decreases as we move down the group.
    In dark
    H2 + F2→ 2HF
    In sunlight
    H2 + Cl2 → 2HCl
    Δ
    H2 + Br2 → 2HBr
    Δ
    H2 + I2→ 2HI

  • 3. REACTION WITH OXYGEN

  • Halogen combines with oxygen to form halogen oxides, but they are not steady. The general formula for oxides is X2O to X2O7 .


  • 4. REACTION WITH METALS

  • Halogens react with metals instantly due to their high reactivity to form metal halides.
    Sodium reacts with chlorine to form sodium chloride which releases a large amount of heat energy and yellow light as it is an exothermic reaction.

    2Na(s) + Cl2 (g) → 2NaCl(s)
    Metal halides are ionic in nature due to the high electronegativity of halogen and electro positivity of metals. The ionic character decreases down the group.

  • 5. REACTION WITH OTHER HALOGENS

  • Halogens form interhalogens when the react with other halogens. The general formula of interhalogens is XYn, where n = 1, 3, 5 or 7. Here X is the less electronegative halogen and Y is the more electronegative halogen.
    XY XY3XY5 XY7
    ClF, BrF, BrCl, ICI, IBr, IFCIF3 BrF3 IF3, ICI3BrF5IF7

    ANOMALOUS BEHAVIOUR OF FLUORINE
    Fluorine illustrates anomalous behavior in properties such as bond dissociation energy, ionization energy, electrode potentials, electro-negativity, electron gain enthalpy, ionic and covalent radii, melting point, and boiling point because of its low bond dissociation energy, small nuclear size. high electronegativity and absence of d-orbital in the valence shell of fluorine.

    APPLICATIONS OF HALOGENS

  • 1. FLUORINE

  • • Fluorine is used in drinking water and toothpaste as it reduces tooth decay

  • • It is present in the clay used in ceramics

  • • They are present in chlorofluorocarbons that are used as refrigerants

  • • They are used to generate nuclear power

  • 2. Chlorine

  • • Chlorine is used to purify drinking water and swimming pools

  • • It is present in PVC (wire insulation

  • • It is used to sterilize hospital machinery

  • • It is also a key factor of certain pesticides like DDT (dichlorodiphenyltrichloroethane)

  • 3. Bromine

  • • Bromine has fire resistant properties, so it is used to retard flames like a fire extinguisher

  • • It is used to treat pneumonia and Alzheimer's disease.

  • • Methyl bromide is a pesticide that is used to eliminate the spread of bacteria and allows for crop storage

  • 4. Iodine

  • • It has a major role in the functioning of the thyroid gland of our body

  • • Solutions used to clean open wounds contain iodine

  • • Silver iodide is used in photography

  • 5. Astatine

  • • Astatine is radioactive

  • • It has helped in the study of cancer