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Werner's theory of coordination compounds - class-XII

Description: werner's theory of coordination compounds
Number of Questions: 32
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Tags: chemistry coordination compounds coordination chemistry d- and f- block elements & coordination compounds
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Among the following complexes (K-P) :
$K _3[Fe(CN _6]-K  $ and $  [Co(NH _3) _6]Cl _3-L$ ; 
$Na _3[Co(oxalate) _3]-M $ and    $  [Ni(H _2O) _6]Cl _2-N$ ;
$K _2[Pt(CN) _4]-O$ and $[Zn(H _2O) _6](NO _3) _2 - P$;
the diamagnetic complexes are:

  1. K,L,M,N

  2. K,M,O,P

  3. L,M,O,P

  4. all 


Correct Option: C
Explanation:

$K _3[Fe(CN _6]-K  $ = $ 3d^5$ it is paramagnetic 


 $  [Co(NH _3) _6]Cl _3-L$ = $3d^6$ is diamagnetic

$Na _3[Co(oxalate) _3]-M $ = $3d^6$ is diamagnetic 

 $  [Ni(H _2O) _6]Cl _2-N$ = $3d^8$ is paramagnetic

$K _2[Pt(CN) _4]-O$ = $d^3 $ it is diamagnetic

 and $[Zn(H _2O) _6](NO _3) _2 - P$;= $ d^6$ it is diamagnetic

According to Werner's coordination theory, there are _______ kinds of valency, _______ and ___. The primary valency of a central metal ion is satisfied with _____.

  1. three, negative, positive, cations

  2. different, negative, positive, anions

  3. two, primary, secondary, anions

  4. two, saturated, unsaturated, cations


Correct Option: C
Explanation:

According to Werner's coordination theory, there are two kinds of valency, primary and secondary. The primary valency of a central metal ion is satisfied with anions.
For example, in $[Cu(NH _3) _4]SO _4$ primary valency is 2 and secondary valency is 4.
Secondary valence refers to coordination number. Since copper is coordinated to 4 ammonia ligands, secondary valence is 4. Primary valence is satisfied by anions. Since sulphate ion has $-2$ charge, primary valence is 2.

Which of the following sets of examples and geometry of the compounds is not correct?

  1. Octahedral - $[Co(NH _3) _6]^{3+}, [Fe(CN) _6]^{3-}$

  2. Square planar - $[Ni(CN) _4]^{2-}, [Cu(NH _3) _4]^{2+}$

  3. Tetrahedral- $[Ni(CO) _4], [ZnCl _4]^{2-}$

  4. Trigonal bipyramidal - $[Fe(NH _3) _6]^{2+}, [CuCl _4]^{2-}$


Correct Option: D
Explanation:

$[Fe(NH _3) _6]^{2+}=Fe^{2+}=[Ar]3d^6=$ Octahedral.

Hybridisation is $=sp^3d^2$ .

$[CuCl _4]^{2+}=Cu^{2+}=[Cu]3d^{9}=$ Tetrahedral.
Hybridisation $=$ $sp^3$

These two do not have trigonal bipyramidal geometry.

Which of the following complexes will have a tetrahedral shape?

  1. $[PdCl _4]^{2-}$

  2. $[Pd(CN) _4]^{2-}$

  3. $[Ni(CN) _4]^{2-}$

  4. $[NiCl _4]^{2-}$


Correct Option: D
Explanation:

$[NiCl _4]^{2-}=$ $Cl^-\rightarrow $ Weak field ligand.

$\Rightarrow Ni^{2+}\Rightarrow [Ar]3d^8$
As the ligands is weak field ligands the complex has tetrahedral geometry of $sp^3$ hybridisation.

The two isomers X and Y with the formula $Cr(H _2O) _5ClBr _2$ were taken for experiment on depression in freezing point. It was found that one mole of X gave depression corresponding to $2$ moles of particles and one mole of Y gave depression due to $3$ moles of particles. The structural formulae of X and Y respectively are:

  1. $[Cr(H _2O) _5Cl]Br _2$; $[Cr(H _2O) _4Br _2]Cl\cdot H _2O$

  2. $[Cr(H _2O) _5Cl)]Br _2$; $[Cr(H _2O) _3ClBr]\cdot 2H _2O$

  3. $[Cr(H _2O) _5Br]BrCl$; $[Cr(H _2O) _4ClBr]Br\cdot H _2O$

  4. $[Cr(H _2O) _4Br _2]Cl\cdot H _2O$; $[Cr(H _2O) _5Cl]Br _2$


Correct Option: D
Explanation:

$Cr(H _2O) _5ClBr _2\longrightarrow$ 2 moles of particle.

It compoubnd is $[Cr(H _2O) _4(Br _2)]Cl.H _2O$
It gives $[Cr(H _2O) _4Br _2]^{+},C\bar l\Rightarrow $ Two particles.
So, $X=[Cr(H _2O) _4Br _2]Cl.H _2O$
If $Y=[Cr(H _2O) _5Cl]Br _2$
It gives $[Cr(H _2O) _5Cl^{2+},2B\bar r\Rightarrow $ 3 particles.

Number of chlorides satisfying secondary valency in $CoCl _{3},\ 4NH _{3}$

  1. $1$

  2. $2$

  3. $3$

  4. $6$


Correct Option: B

The secondary valency of Chromium in $[Cr(en) _3]CI _3$ is

  1. 6

  2. 3

  3. 2

  4. 4


Correct Option: A

According to Werner’s theory of valency transition metals possesses:

  1. only one type of valency

  2. two types of valencies

  3. three types of valencies

  4. four types of valencies


Correct Option: B
Explanation:

According to Werner’s theory of valence, transition metals has two valencies are primary valencies and secondary valency.
Primary valencies are those which are statisfied by ligands through coordination bonds and charge that remained on the coordination sphere is satisfied by secondary valence.


Hence, the correct option is $B$

Which of the following alkaline earth metal sulphates has hydration enthalpy higher than the lattice enthalpy ?

  1. $SrSO _2$

  2. $MgSO _2$

  3. $CaSO _4$

  4. None


Correct Option: B

The co-ordination number of a metal in co-ordination compound is:

  1. same as primary valency

  2. sum of primary and secondary valences

  3. same as secondary valency

  4. none of the above


Correct Option: C
Explanation:

The secondary valency is equal to the coordination number the secondary valency are non ionizable valencies. These are satisfied by neutral molecules or negative ions.  For example in $[Ni(CO) _4]$ the coordination number of Ni metal is four and its secondary valency is also four.

How many of the following metals when heated in an atmosphere of N2 gas form nitrides ?
Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba

  1. 9

  2. 5

  3. 3

  4. 6


Correct Option: B

1 mole of co-ordinate compound $CoCl _3$ on reaction with excess AgNCl $143.5$gms of AgCl ppt . Then number of chloride ions satisfying both primary valency and secondary valency are?

  1. $2$

  2. $3$

  3. $1$

  4. $0$


Correct Option: A
Explanation:

Moles of $AgCl$ formed $=\cfrac{143.5}{143.5}=1$

$1$ mole of $CoCl _3$ gives $1$ mol of $AgCl$ ppt.
Secondary valence is the number of ions that are coordinated to metal ion. Here, $1Cl^-$ ion is not coordinated to the metal ion, due to which it gives $AgCl$ ppt. Hence, no. of chloride ions satisfying the given condition $=2.$

According to Werner's theory the primary valency and secondary valency in complex $[Co(NH _3) _4Cl _2]Cl$ is respectively:

  1. 3,3

  2. 3, 6

  3. 6, 3

  4. 4, 2


Correct Option: B
Explanation:

The primary valency is the oxidation state of the metal ion and the coordination number of the metal is the secondary valency of the metal ion. 


The oxidation number of $Co = x + 0 -3 = 0$

                                           $x = 3$

The primary valency is 3 and the secondary valency is 6. Therefore, the correct option is B.

Which of the following is not correctly matched ? 

  1. $[Fe (CN) _6]^{3-} d^2 sp^3$, paramagnetic

  2. $[Ni (CO) _4] -sp^3$, diamagnetic

  3. $[Fe(en) _3]^{+3} - sp^3 d^2$, paramagnetic

  4. $[FeCl _2 (H _2O) _2] sp^3$, paramagnetic


Correct Option: A

According to Werner's theory state which of the following statements are correct:


1. Ligands are connected to the metal ions by covalent bonds
2. Secondary valencies have directional properties
3. Secondary valencies are non-ionisable.

  1. 1, 2, and 3 are correct

  2. 2 and 3 are correct

  3. 1 and 2 are correct

  4. 1 ,2 are correct,and 3 is not correct


Correct Option: A

The primary velency of the cemtral transition metal ion in comlex compounds $[Cr(NH _3) _4CI _2]CI$

  1. 3

  2. 2

  3. 1

  4. 0


Correct Option: A

Select correct statement about "Ziese's salt' $K[PtCI _{3}(n^ {2}-C _{2}H _{4})]$

  1. It has only two types of $M-CI$ bond length

  2. $E.A.N=84$

  3. It's $\pi$ Bonded $O.M.C$

  4. $All\ of\ these$


Correct Option: D

The primary valency of iron in ${{\text{K}} _{\text{4}}}\left[ {{\text{Fe}}{{\left( {{\text{CN}}} \right)} _{\text{6}}}} \right]$ is 

  1. 1

  2. 2

  3. 3

  4. 4


Correct Option: B

The units of solubility product of silver chromate $(Ag 2CrO _4)$ will be _________.

  1. $mol^2L^{-2}$

  2. $mol^3L^{-3}$

  3. $mol L^{-1}$

  4. $mol L^{-2}$


Correct Option: C
Explanation:
 Molar solubility is the number of moles of a substance (the solute) that can be dissolved per liter of solution before the solution becomes saturated. It can be calculated from a substance's solubility product constant (Ksp) and stoichiometry. The units are mol/L, sometimes written as M.

In $CuSO _4.5H _2O$ how many molecules of water are indirectly connected to Cu? 

  1. $5$

  2. $4$

  3. $2$

  4. $1$


Correct Option: D
Explanation:

Solution:- (D) $1$

In $CuSO _4.5H _2O$, Four water molecules form coordinate bond with $Cu _{2+}$ ion while one water molecule is associated with $H$- bond

The primary valence of the metal ion is satisfied by :

  1. neutral molecules

  2. positive ions

  3. negative ions

  4. all


Correct Option: C
Explanation:

The primary or principal valency; this is the ionisable valency. 


A metal always gives electron and becomes positively charged that can be neutralized by bonding with negative ion only. In a coordination compound, the number of negative ions needed to satisfy the charge on the central metal ion is it's  primary valency.

Secondary valencies correspond to ____________ of the metal atom and are satisfied by ligands.

  1. coordination number

  2. valency

  3. element

  4. molecules


Correct Option: A
Explanation:

 Secondary valency corresponds to the coordination number of central metal atom or ion. This may be satisfied by either negative ions or neutral molecules called ligands.

 Ligands satisfying the secondary valencies are always shown in square brackets, i.e. they form the coordination sphere of the metal atom.


Hence,option A is correct.

$2.33$g of compound X(empirical formula $CoH _{12}N _4Cl _3)$ upon treatment with excess $AgNO _3$ solution produces $1.435$g of a white precipitate. The primary and secondary valences of cobalt in compound X, respectively, are.
[Given : Atomic mass: $Co=59, Cl=35.5, Ag=108$].

  1. $3, 6$

  2. $3, 4$

  3. $2, 4$

  4. $4, 3$


Correct Option: A
Explanation:

Since $0.01$ mole of $X$ produces $0.01$ mole of $AgCl$,hence one $Cl^-$ is out of coordination sphere or complex is $[CO(NH _3) _4Cl _2]Cl$ AND HENCE $CO(3+)$,has $6$ coordination number

Several octahedral complexes are possible from combinations of $Co^{3+}, Cl^{-}$ and $NH {3}$. The correct statement(s) regarding the octahedral coordination entities having the formula .$[Co(NH _{3}) _{n}Cl _{6 - n}]^{(n - 3)+}$ with $n\geq 3$, is/ are____________.

  1. At most six octahedral complexes are possible

  2. One of the complexes is homoleptic

  3. All the complexes are paramagnetic

  4. Some of the complexes dissociate in water to give $Co^{3+}$ and $Cl^{-}$ ions


Correct Option: A,B
Explanation:

$[Co(NH _3) _nCl _{6-n}]^{(n-3)^+}$  $n\ge 3$

For $n=3,n=4,n=5,n=6$
For $n=6\Rightarrow [Co(NH _3) _6]^{3+}=$ is  homopletic due to all 6 same ligands.
For $n=5\Rightarrow [Co(NH _3) _6]^{2+}$
For $n=4\Rightarrow [Co(NH _3) _6]^+=$
For $n=3\Rightarrow [Co(NH _3) _6]$
Only $4$ octahedral complex are possible.
One of them is homoleptic.

In the separation of $Cu^{2+}$ and $Cd^{2+}$ in the second group of qualitative analysis of cations, tetraamine copper (ll) sulphate and tetraamine cadmium (ll) sulphate react with KCN to form corresponding cyano complexes. Which of the following pairs of complexes and their relative stability enables the separation of $Cu^{2+}$ and $Cd^{2+}$?

  1. $K _2[Cu(CN) _4]$ is less stable and $K _2[Cd(CN) _4]$ is more stable

  2. $K _3[Cu(CN) _4]$ is more stable and $K _2[Cd(CN) _4]$ is less stable
  3. $K _3[Cu(CN) _4]$ is less stable and $K _2[Cd(CN) _4]$ is more stable
  4. $K _2[Cu(CN) _4]$ is more stable and $K _2[Cd(CN) _4]$ is less stable


Correct Option: B

Primary and secondary valency of platinum in the complex $[Pt(en) _{2}Cl _{2}]$ are:

  1. $4,6$

  2. $2,6$

  3. $4,4$

  4. $2,4$


Correct Option: B,D
Explanation:

The Given complex $[Pt(en) _2Cl _2]$ The primary valence is its oxidation number i.e +2 and the secendory valency is its coordination number i.e 6 in this case.(The en ligand is bidentate, and Cl is monodentate).The second possibility  is that compound can exist as $[Pt(en) _2]Cl _2$ and hence the primary valency can also be +2 and  secondary valence is 4. Hence option B and D are correct

The Alsatian-Swiss chemist Alfred Werner pioneered the field of coordination chemistry in the late nineteenth century. At that time, a number of compounds of cobalt (III) chloride with ammonia were known, with general formula $CoCl _3.xNH _3$ $x=3\ to\ 6$
Treatment of these compounds with aqueous HCl acid did not remove the ammonia. However, treatment of the compounds with excess of $AgNO _3$ at 273 K gave white precipitate of AgCl in varying ratio depending on the structure. Also each complex had electrical conductivity of varying nature.
 
There is no reaction of the compound with aqueous HCl indicating that there is no free $NH _3$. Thus, $NH _3$ ligand is bonded to cobalt(III) by________ .
  1. Primary valency.

  2. Secondary valency.

  3. Both of these.

  4. None of these.


Correct Option: B
Explanation:
Option (B) is correct.

Thus, $NH _3$ ligand is bonded to cobalt$(III)$ by secondary valency. Ammonia is present inside the coordination sphere and does not ionises while chloride ions present outside the sphere reacts with $AgNO _3$

$[Co(NH _3) _5Cl]Cl _2 + AgNO _3 \longrightarrow [Co(NH _3) _5Cl](NO _3) _2 + AgCl _2$

How many EDTA (ethylenediaminetetraacetic acid) molecules are required to make an octahedral complex with $ Ca^{2+} $?

  1. six

  2. three

  3. one

  4. two


Correct Option: C
Explanation:

An octahedral complex has 6 bonds around the central atom . One EDTA moledule complexes with one molecule of calcium cation to form octahedral complex.

which has the maximum conductivity in thier 0.1M solution?

  1. A) $\left[ Co{ (NH } _{ 3 }) _{ 3 }{ Cl } _{ 3 } \right] $

  2. B) $\left[ Co({ NH } _{ 3 }) _{ 4 }Cl \right] { Cl } _{ 2 }$

  3. C) $\left[ Co({ NH } _{ 3 }) _{ 5 }Cl \right] { Cl } _{ 2 }$

  4. D) $\left[ Co({ NH } _{ 3 }) _{ 6 } \right] { Cl } _{ 3 }$


Correct Option: D
Explanation:

The maximum conductivity is shown by that compound which have maximum ions on dissociation. Hence the compound $[Co(NH _3) _6]Cl _3$ have the maximum number of ions $[Co(NH _3) _6] + 3Cl^-$ = 4 ions and hence the correct answer is D.

The number of complexes that can be can be made with varying $NH _3$ ligands to satisfy primary and secondary valencies of platinum are:

Complex; [$PtCl _4\cdot xNH _3$]   

  1. 5

  2. 3

  3. 4

  4. 2


Correct Option: A
Explanation:
The correct answer is 5.
The number of complexes that can be can be made with $PtCl _4\cdot xNH _3$ are :
 
I. $[Pt(NH _3) _6]Cl _4$

II. $[Pt(NH _3) _5Cl]Cl _3$

III. $[Pt(NH _3) _4Cl _2]Cl _2$

IV: $ [Pt(NH _3) _3Cl _3]Cl$

V: $[Pt(NH _3) _2Cl _4]$

Option A is correct.

Which of the following statement(s) is/are correct?

  1. Primary valency of the central metal of a complex is always satisfied by anions.

  2. Secondary valency of the central metal of a complex may be satisfied by either negative ions or neutral molecules.

  3. Species which show primary valencies in a complex compound can be precipitated out.

  4. None of the above


Correct Option: A,B,C
Explanation:

In short the Werner's theory may be stated as follows:

  1. The central metal in a complex possesses two types of valencies, primary or ionizable valency and secondary valency or non-ionizable valency.
  2. While the primary valency of the metal is variable, the secondary valency has a fixed value. The primary valency refers to the oxidation state and the secondary valency to the coordination number of the metal.
  3. The primary valency is satisfied by only negative ions whereas the secondary valency either by anions or neutral molecules or both.
  4. The secondary valencies are directed in space towards fixed positions around the neutral atom.
Hence, options A, B and C are correct.

When $AgNO _3$ is added to a solution of $Co(NH _3) _5 Cl _3$, the precipitate of $AgCl$ shows two ionized chloride ions. This means:

  1. only two chlorine atoms satisfy primary valency and one secondary valency

  2. one chlorine atom satisfies primary as well as secondary valency

  3. two chlorine atoms satisfy primary valency

  4. three chlorine atoms satisfy secondary valency


Correct Option: B,C
Explanation:

Option (B),(C) are correct.
When $AgNO _3$ is added to a solution of $Co(NH _3) _5 Cl _3$, the precipitate of $AgCl$ shows two ionized chloride ions.This means one chlorine atom satisfies primary as well as secondary valency and two chlorine atoms satisfy primary valency. Hence, $Co(NH _3) _5 Cl _3$, can be written as $[Co(NH _3) _5 Cl]Cl _2$,

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