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Sunday, July 25, 2021

Oxy-acids of Phosphorous:

Oxy acids of Phosphorous:

On the basis of oxidation state oxidation state of phosphorous atom oxy-acid acid of phosphorous divided into to series;

(1) Phosphorous series of acids have (+3) oxidation state and which are reducing agents.

(2) Phosphoric series of acids have (+5) oxidation state and which are oxidizing agents.

Oxidation state of phosphorous atom and respective oxy-acids:

Oxidation state

 Series name

Prefix of acid

Name of acids

(+1)

“us”series

Hypo

Hypophosphorous acid

(+3)

“us”series

…….

Phosphorous acid

(+4)

“ic”series

Hypo

Hypophosphoric acid

(+5)

“ic”series

…….

Phosphoric acid

(+7)/(+6)Cal/ava

“ic”series

Per

Perphosphoric acid

“Phosphorous and phosphoric acid both exist in ortho, pyro and meta form”

Common structure of oxy-acid of phosphorous:

All the phosphorous acid  out four valency must have one (P=O) group by Ppi-Ppi bond and one (-OH) group and rest of two valency may be satisfied by P-(H) atoms of P-(OH) group depending upon acids. Where hydrogen of (OH) groups are ionizable and reponsible for acidic character while hydrogen of P-(H) bond non ionizable and responsible for reducing character of acid and non acidic.

(1) Phosphorous series:

(A) Hypophosphorus acid (H3PO2): is a monobasic acid and its neutral salt is NaH2PO2. There is two hydrogen atoms directly attach with phosphorous atom which are non ionazable and non polar and responsible for its reducing character and one hydrgen atom attach with oxygen atom and ionizable and polar and also reponsible for acidic character and its basicity is one.

(B) Phosphorus acid (H3PO3): is a dibasic acid and it have two salts one is   neutral salt (Na2HPO2) and another is acidic salt (NaH2PO3).There is one hydrogen atoms directly attach with phosphorous atom which are non ionazable and non polar and responsible for its reducing character and two hydrgen atom attach with oxygen atom and ionizable and polar and also reponsible for acidic character and its basicity is two.

(C) Pyrophophorous acid(H4P2O5):

(2) Phosphoric series:

(A) Phosphoric acid (H3PO4): is a tribasic acid and it have three salts in which one is neutral salt (Na3PO4) and another  two are acidic salt (NaH2PO3) and (Na2HPO4).There are all three hydrgen atoms attach with oxygen atom and ionizable and polar and also reponsible for acidic character and hence its basicity is (3) three. And it is highly viscous in nature due to intermolecular hydrogen bonding in it.

(B) Pyrophosphoric acid(H4P2O7):

(C) Hypophosphoric acid(H4P2O6):

(D)Meta phosphoric acids (HPO3)n: where n=3,4,5,6….. and their salts always exist in dimeric, trimeric, tetrameric or in polymeric linear as well as cyclic form, not in monomeric form due to the presence of weak (2p-3d- pi bond) bond the sodium salts of trimer and hexamer is very famous salts.

For example (1); H6P4O13   (4P+6OH+4O+3O(oxylinkage)

For example (2); H3P3O (3P+3OH+3O+3O(oxy-linkage):

For example (3); H4P4O12   {4P+4OH+4O+4O(oxy-linkage)}:

For example (4); H6P6O18   {4P+6OH+6O+6O(oxy-linkage)}:

Hexamer of meta phosphoric acid exist as sodium salt which is called sodium metaphophate or sodium polymetaphosphate and it is commercially  known as "CALGON" and use as water softener.

Related topics:

Saturday, July 24, 2021

Why Sulphuric acid is more acidic than selenic acid?

Acidic strength of oxyacids H2SO4 and H2SeO4. Sulphur and Selenium belong to group sixteen in the periodic table. Sulphur is more electronegative the selenium and can polarize and weaken the O-H bond to a greater extent than selenium in their oxyacids, making sulphuric acid a stronger acid.

OXY ACIDS:


Friday, July 23, 2021

Slater's Rules: (Estimating the extent of shielding):

The quantitative prediction of specific energy level is not possible if an atom have more than one electron (multi-electrons system). In multi-electron system each electron acts as a shield for electron further away from the nucleus, reducing the attraction between the nucleus and distant electron. The Slater provides a set of rules which help to predict the extent of shielding.

In the Slater rule determine the actual charge felt by an electron and also allow you to estimate the effective nuclear charge Zeff  from the real number of protons in the nucleus and the effective shielding of electrons in each orbital "shell"

“Slater defined Z* or Zeff (effective nuclear charge) as a measure of nuclear attraction for an electron. Or The magnitude of  positive charge “experienced” by an electron in the atom.

                                              Thus Z* =Z-S

Where Z is the (nuclear charge)= The number of protons in the nucleus of an atom,  and S represent the shielding constant and value is greater than zero but less than Z.

Step 1: Write the electron configuration of the atom in the following form:

              (1s) (2s, 2p) (3s, 3p) (3d) (4s, 4p) (4d) (4f) (5s, 5p) . . .

 

Step (2):  Electron in higher group do not shield the electrons in the lower group.

Step (3): For ns and np valence electrons:

(A) The electrons in same ns and np group contribute 0.35, except the 1s which shield 0.30

(B) Electrons within the n-1 group contribute 0.85

(C) Electrons within the n-2 or lower groups contribute (shield) 1.00

Step (4): For nd and nf valence electrons:

(A) Electrons in same nd and nf group contribute 0.35

(B) Electrons in the group to the left contribute 1.00

Shielding constant (S) obtained is subtracted from Z to get Z*

 Solved Questions:

(1) What is the shielding constant (S) experienced by a 3d electron in the bromine atom?

What is the shielding constant (S) experienced by a 3d electron in the bromine atom?

Step (1): Write the electronic configuration of Bromine in the appropriate form.

Br: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5

Br: (1s2)(2s2,2p6)(3s2,3p6)(3d10)(4s2,4p5)

Step (2): Use the Slater Rule to calculate the shielding constant for the electron. And ignore the group of electron to the right of the 3d electrons, these electrons do not contribute to the shielding constant.

(S)3d = (d electrons-1)x 0.35+ (remaining electrons)x1.00= 21.15

(S)3d = (10-1)x 0.35+ (18)x1.00= 21.15

Solved Questions:

(2) A given compound AB whose electronegative difference is 1.9 . Atomic radius of A and B are 4 and 2 Angstroms the distance between A and B means dA-B is ?

(3) Stevenson & Schromaker Equation: Determination covalent radius of Heterogeneous Molecules.


Related Questions:

(1) What are the Amphoteric metals ? gives Examples.

(2) Name of total metalloids present in periodic table ?

(3) Total numbers of elements which are liquid at normal temperature is ?

(4) What is Mendeleev's periodic table ? give important features and draw back of Mendeleev's table.

(5) What is atomic density ? give the periodicity of atomic density in periods and groups.

(6) What is atomic volume ? and what is periodicity of atomic volume in groups and periods ?

(7) Why there are 2, 8 and 8 elements in first, second and third periodic of periods table respectively ? Explain.

(8) In alkali metal group which is the strongest reducing agent in aqueous solution and why?

(9) The electron affinity of sulphur is greater than oxygen. Why?

(10) The first ionization energy of carbon atom is greater than that of boron atom, whereas reverse is true for the second ionization energy. Explain.

The electronegativity of F and H are 4.0 and 2.1 respectively. The percentage ionic character in H and F bond is.

The percentage ionic character in covalent compound arises due to the electronegative difference of bonding atoms. And percentage ionic character of covalent bond calculates by Henry and Smith equation;

Solved Questions:

Related Questions:

(1) The electronegativities of B, Al, Ga are 2.0, 1.5, 1.6 respectively. The trend is not regular. Explain.

(2) Li2CO3 decomposes on heating but other alkali metal carbonates don’t. Explain.

(3) Of all noble metals, gold has got a relatively high electron affinity. Explain.

(4 Ionization energy of Boron is smaller than Beryllium even though effective nuclear charge is higher?

(5) What are the increasing order of ioni radii of first group elements in water ?

(6) What are the increasing order of molar conductivity of first group elements in water ?