Inorgnic

2013 unit 1

Explain on the basis of valence bond theory that [Ni(CN)4]2- ion with square
planar structure is diamagnetic and the [Ni(CN)4]2- ion with tetrahedral
geometry is paramagnetic.
Answer

Ni is in the +2 oxidation state i.e., in d8 configuration.

There are 4 CN- ions. Thus, it can either have a tetrahedral geometry or square planar geometry.
Since CN- ion is a strong field ligand, it causes the pairing of unpaired 3d electrons.

It now undergoes dsp2 hybridization. Since all electrons are paired, it is diamagnetic.
In case of [Ni(CN)4]2- , Cl- ion is a weak field ligand. Therefore, it does not lead to the pairing of
unpaired 3d electrons. Therefore, it undergoes sp3 hybridization.

Since there are 2 unpaired electrons in this case, it is paramagnetic in nature.

what is spectrochemical series and ho has it been obtained

what is d-d transition?

In a dd transition, an electron in a d orbital on the metal is excited by a photon to another d orbital of higher energy.
In complexes of the transition metals, the d orbitals do not all have the same energy. In centrosymmetric
complexes, d-d transitions are forbidden by the Laporte rule

Why are d-d electronic transitions forbidden and

weakly absorbing? Why do they occur at all?
1 Answer
In order for an electronic transition to be allowed (occur with strong intensity), certain "selection rules" must be obeyed.
You may already be familiar with the rule that the electron spin quantum number cannot change during a transition. It is
this rule that forbids singlet-to-triplet absorption or emission (emission follows the same rules as absorption) and
consequently makes phosphorescent emission so much weaker than fluorescent emission.

S=0S=0 the Spin rule

Another rule, often referred to as the "LaPorte" rule or the "Orbital" rule, states that in molecules with a center of
symmetry (centrosymmetric molecules), transitions within a subshell are forbidden when l=0l=0.
l=1l=1 the LaPorte rule
The orbital angular momentum quantum number "l" describes the type of orbital (s, p, d, f) within the subshell. In
centrosymmetric molecules, the various s, p, d, f orbitals cannot mix within a subshell. For example, the 4d orbital cannot
mix with the 4p orbital in a centrosymmetric molecule, such mixing being symmetry forbidden. Octahedral complexes
can be centrosymmetric. In such a case 3p->3p, 3d->3d transitions would be forbidden by LaPorte's rule. Tetrahedral
molecules do not have a center of symmetry and p-d orbital mixing is allowed, so in the case of tetrahedral molecules 3p-
>3p and 4d->4d transitions may appear stronger because a small amount of another orbital may be mixed into the p or d
orbital thereby removing the violation of LaPorte's rule.

If we can do something to remove the centrosymmetric nature of an octahedral complex, then we "relax" LaPortes rule
and weak transitions can be observed. For example, if a molecular vibration removes the molecular center of symmetry,
then a d->d transition can occur if light is absorbed at that instant. Things such as spin-orbit coupling, vibronic coupling,
or ligands that can mix with the metal's d orbitals would all allow relaxation of LaPorte's rule and thereby permit weak
transitions to be observed

2015

explain high spin & low spin complexes in terms of CFT of octahedral complexes?

Octahedral Geometry
Octahedral geometry is still harder to visualize because of how many ligands it contains. Octahedral
geometry can be visualized in two ways: it can be thought of as two pyramids stuck together on their bases
(one pyramid is upright and the other pyramid is glued to the first pyramid's base in an upside down
manner) or it can be thought of as a molecule with square planar geometry except it has one ligand sticking
out on top of the central molecule and another ligand sticking out under the central molecule (like a jack).
Finally, the bond angle between the ligands is 90o. An example of the octahedral molecule SF6 is provided
below.
2013

Unit 3

Flame Photometry: Its Principle, Instrumentation & Applications

Flame photometry is a process where in emission of radiation by neutral atoms is measured.

The neutral atoms are obtained by introduction of sample into flame. Hence the name flame photometry.

Since radiation is emitted it is also called as flame emission spectroscopy.

FLAME PHOTOMETER WORKING PRINCIPLE:
When a solution of metallic salt is sprayed as fine droplets into a flame. Due to heat of the flame, the droplets dry leaving a fine residue
of salt. This fine residue converts into neutral atoms.

Due to the thermal energy of the flame, the atoms get excited and there after return to ground state. In this process of return to ground
state, exited atoms emit radiation of specific wavelength. This wavelength of radiation emitted is specific for every element.

This specificity of wavelength of light emitted makes it a qualitative aspect. While the intensity of radiation, depends on the
concentration of element. This makes it a quantitative aspect.
The process seems to be simple and applicable to all elements. But in practice only a few elements of Group IA and group IIA (like Li,
Na, k & Ca, Mg) are only analyzed.
The radiation emitted in the process is of specific wavelength. Like for Sodium (Na) 589nm yellow radiation, Potassium 767nm range
radiation.
FLAME PHOTOMETER INSTRUMENTATION:
1.Burner
2.Monochromators
3.Detectors
4. Recorder and display.

Burner: This is a part which produces excited atoms. Here the sample solution is sprayed into fuel and oxidant combination. A
homogenous flame of stable intensity is produced.

Total Consumption burner

There are different types of burners like Total consumption burner, Laminar flow and Mecker burner.

Fuel and oxidants: Fuel and oxidant are required to produce flame such that the sample converts to neutral atoms and get excited by
heat energy.
The temperature of flame should be stable and also ideal. If the temperature is high, the elements in sample convert into ions instead of
neutral atoms. If it is too low, atoms may not go to exited state. So a combination of fuel and oxidants is used such that there is desired
temperature.
The following combination of fuel and oxidants are commonly used.
Fuel Oxidant Temperature of Flame

Propane + Air 2100 Degree C

Propane + Oxygen 2800 Degree C

Hydrogen + Air 1900 Degree C

Hydrogen + Oxygen 2800 Degree C

Acetylene + Air 2200 Degree C

Acetylene + Oxygen 3000 Degree C

Monochromators:
Filters and monochromators are needed to isolate the light of specific wavelength from remaining light of the flame. For this simple
filters are sufficient as we study only few elements like Ca, Na, K and Li. So a filter wheel with filter for each element is taken. When a
particular element is analyzed, the particular filter is used so that it filters all other wavelengths.
Detector: Flame photometric detector is similar to that used in spectrophotometry. The emitted radiation is in the visible region i.e.
400nm to 700nm. Further the radiation is specific for each element so simple detectors are sufficient for the purpose like photo voltaic
cells, photo tubes etc.
Recorders and display: These are he devices to read out the recording from detectors.
 Flame photometer uses/ Applications
1. For qualitative analysis of samples by comparison of spectrum emission wavelengths with that of standards.
2. For quantitative analysis to determine the concentration of group IA and IIA elements. For example
a) Concentration of calcium in hard water.
b) Concentration of Sodium, potassium in Urine
c) Concentration of calcium and other elements in bio-glass and ceramic materials.
Flame photometry limitations:
Unlike other spectroscopy methods, flame photometry finds little use in research and analysis. This is due to
1. Limited number of elements that can be analyzed.
2. The sample requires to be introduced as solution into fine droplets. Many metallic salts, soil, plant and other compounds are insoluble in
common solvents. Hence, they cant be analyzed by this method.
3. Since sample is volatilized, if small amount of sample is present, it is tough to analyze by this method. As some of it gets wasted by
vaporization.
4. Further during solubilisation with solvents, other impurities might mix up with sample and may lead to errors in the spectra observed.

what is ion exchanger?what are its types ?write two uses of ion exchenger

on exchange is an exchange of ions between two electrolytes or between an electrolyte solution and a complex. In most
cases the term is used to denote the processes of purification, separation, and decontamination of aqueous and other ion-
containing solutions with solid polymeric or mineralic 'ion exchangers'.

Typical ion exchangers are ion exchange resins (functionalized porous or gel polymer), zeolites, montmorillonite, clay,
and soilhumus. Ion exchangers are either cation exchangers that exchange positively charged ions (cations) or anion
exchangers that exchange negatively charged ions (anions). There are also amphoteric exchangers that are able to
exchange both cations and anions simultaneously. However, the simultaneous exchange of cations and anions can be
more efficiently performed in mixed beds that contain a mixture of anion and cation exchange resins, or passing the treated
solution through several different ion exchange materials.

Ion exchanges can be unselective or have binding preferences for certain ions or classes of ions, depending on
theirchemical structure. This can be dependent on the size of the ions, their charge, or their structure. Typical examples of
ions that can bind to ion exchangers are:

H+ (proton) and OH (hydroxide)

Single-charged monatomic ions like Na+, K+, and Cl
Double-charged monatomic ions like Ca2+ and Mg2+
Polyatomic inorganic ions like SO42 and PO43
Organic bases, usually molecules containing the amine functional group -NR2H+
Organic acids, often molecules containing -COO (carboxylic acid) functional groups
Biomolecules that can be ionized: amino acids, peptides, proteins, etc.

Along with absorption and adsorption, ion exchange is a form of sorption.

Ion exchange is a reversible process and the ion exchanger can be regenerated or loaded with desirable ions by washing
with an excess of these ions.

Types

There are three steps are of absolute importance:

1) Swelling of medium: (Pre-cycling):

Swelling makes the functional groups to be exposed for ion exchange.

Swellimg of anion exchangers is usually carried out by treating it. first with an acid (0.5N HCl) and then with base (0.5N
NaOH).
Exactly the reverse is the case with cationic exchangers. The matrix can be treated with EDTA for impurity eliminations.
2) Removal of very small particles:
These fines will decrease flow rate and unsatisfactory reaction. To remove fines, the exchanger is repeatedly suspended
in a large volume of water and after the larger polymers have settle down, the slow sedimenting materials decanted.

3) Equilibration with counter ions:

This is accomplished by washing the exchanger with different reagents depending upon the desired counter ion to be
introduced.

NaOH > counter ion to be introduced is Na+

HCl > counter ion to be introduced is H+
NaNO3 > counter ion to be introduced is NO3

USE

Applications of Ion Exchange Chromatography:

1. It is extremely used in the analysis of amino acids. The amino acid Autoanalyzer is based on in exchange
principle.
2. To determine the base composition of nucleic acids. Chargaff used this technique for established the equivalence
of Adenine and Thymine; Guanine and Cytosine.
3. This is most effective method for water purification. Complete deionization of water (or) a non-electrolyte
solution is performed by exchanging solute cations for hydrogen ions and solute anions for hydroxyl ions. This is
usually achieved by method is used for softening of drinking water.
4. Proteins are also successfully separated by this technique.
5. It is also used for the separation of many vitamins, other biological amines, and organic acids and bases.
DISCUSS THE PRINCIPLE OF colorimetric estimation
estimation of metal ion like Fe3+ion explain

Pdf

DISCUSS THE PRINCIPLE OF ditermination of na+ or k+ ion content of solution by flame photomtric
method of analysis

Flame Photometry .

Theory

Procedure

Self Evaluation

Simulator
Animation

Assignment

Reference

Feedback

Objective:

To determine the concentration of alkali and alkaline earth metals in various samples.

Introduction

Atomic spectroscopy is thought to be the oldest instrumental method for the determination of elements. These
techniques are introduced in the mid of 19th Century during which Bunsen and Kirchhoff showed that the
radiation emitted from the flames depends on the characteristic element present in the flame. The potential of
atomic spectroscopy in both the qualitative as well as quantitative analysis were then well established. The
developments in the instrumentation area led to the widespread application of atomic spectroscopy. Atomic
spectroscopy is an unavoidable tool in the field of analytical chemistry. It is divided into three types which are
absorption, emission, and luminescence spectroscopy. The different branches of atomic absorption spectroscopy
are (1) Flame photometry or flame atomic emission spectrometry in which the species is examined in the form of
atoms (2) Atomic absorption spectrophotometry, (AAS), (3) Inductively coupled plasma-atomic emission
spectrometry (ICP-AES).

Gustav Kirchhoff (left) and Robert Bunsen (right)

Theory:

Photoelectric flame photometry, a branch of atomic spectroscopy is used for inorganic chemical analysis for
determining the concentration of certain metal ions such as sodium, potassium, lithium, calcium, Cesium, etc. In
flame photometry the species (metal ions) used in the spectrum are in the form of atoms. The International
Union of Pure and Applied Chemistry (IUPAC) Committee on Spectroscopic Nomenclature has recommended it as
flame atomic emission spectrometry (FAES). The basis of flame photometric working is that, the species of alkali
metals (Group 1) and alkaline earth metals (Group II) metals are dissociated due to the thermal energy provided
by the flame source. Due to this thermal excitation, some of the atoms are excited to a higher energy level where
they are not stable. The absorbance of light due to the electrons excitation can be measured by using the direct
absorption techniques. The subsequent loss of energy will result in the movement of excited atoms to the low
energy ground state with emission of some radiations, which can be visualized in the visible region of the
spectrum. The absorbance of light due to the electrons excitation can be measured by using the direct absorption
techniques while the emitting radiation intensity is measured using the emission techniques. The wavelength of
emitted light is specific for specific elements.

Flame Photometer

Parts of a flame photometer

1. Source of flame:
A burner that provides flame and can be maintained in a constant form and at a constant temperature.

2. Nebuliser and mixing chamber:

Helps to transport the homogeneous solution of the substance into the flame at a steady rate.

3. Optical system (optical filter):

The optical system comprises three parts: convex mirror, lens and filter. The convex mirror helps to
transmit light emitted from the atoms and focus the emissions to the lens. The convex lens help to focus
the light on a point called slit. The reflections from the mirror pass through the slit and reach the filters.
This will isolate the wavelength to be measured from that of any other extraneous emissions. Hence it acts
as interference type color filters.

4. Photo detector:
Detect the emitted light and measure the intensity of radiation emitted by the flame. That is, the emitted
radiation is converted to an electrical signal with the help of photo detector. The produced electrical signals
are directly proportional to the intensity of light.

A schematic representation of flame photometer is shown in figure 1,

 Fig 1: A schematic representation of flame photometer

Mechanism of working:

The working of the flame photometer involves a series of steps which is discussed in the following sections.

Nebulisation:

The solution of the substance to be analyzed is first aspirated into the burner, which is then dispersed into the
flame as fine spray particles.

A brief overview of the process:

1. The solvent is first evaporated leaving fine divided solid particles.

2. This solid particles move towards the flame, where the gaseous atoms and ions are produced.
3. The ions absorb the energy from the flame and excited to high energy levels.

4. When the atoms return to the ground state radiation of the characteristic element is emitted.

5. The intensity of emitted light is related to the concentration of the element.

Fig 2: Brief overview of the process

Events occurring in the flame:

Flame photometry employs a variety of fuels mainly air, oxygen or nitrous oxide (N2O) as oxidant. The
temperature of the flame depends on fuel-oxidant ratio.

The various processes in the flame are discussed below:

Desolvation: The metal particles in the flame are dehydrated by the flame and hence the solvent is evaporated.
Vapourisation: The metal particles in the sample are dehydrated. This also led to the evaporation of the
solvent.
Atomization: Reduction of metal ions in the solvent to metal atoms by the flame heat.
Excitation: The electrostatic force of attraction between the electrons and nucleus of the atom helps them to
absorb a particular amount of energy. The atoms then jump to the exited energy state.
Emission process: Since the higher energy state is unstable the atoms jump back to the stable low energy
state with the emission of energy in the form of radiation of characteristic wavelength, which is measured by the
photo detector.

The energy level diagram of the sodium atom is shown in figure 3

 Fig 3: Energy level diagram for atomic sodium

The intensity of the light emitted could be described by the Scheibe-Lomakin

Scheibe Lomakin equation:

Where:

= Intensity of emitted light

= the concentration of the element

 = constant of proportionality

(at the linear part of the calibration curve)

Then,

That is the intensity of emitted light is directly related to the concentration of the sample.

The comparison of emission intensities of unknown samples to either that of standard solutions (plotting
calibration curve), or to those of an internal standard
standard (standard addition method), helps in the quantitative
analysis of the analyte metal in the sample solution.

The flame emissions of the alkali and alkaline earth metals in terms of the emission wavelength and the
characteristic color produced by each element
e is shown in table 1

Name of the element Emitted wavelength range (nm) Observed colour of the flame

Violet
Potassium (K) 766

Red
Lithium (Li) 670

Orange
Calcium (Ca) 622

Yellow
Sodium (Na) 589
 Lime green
Barium (Ba) 554

Applications:

Flame photometer has both quantitative and qualitative applications. Flame photometer with monochromators
emits radiations of characteristic wavelengths which help to detect the presence of a particular metal in the
sample. This help to determine the availability of alkali and alkaline earth metals which are critical for soil
cultivation. In agriculture, the fertilizer requirement of the soil is analyzed by flame test analysis of the soil. In
clinical field, Na+ and K+ ions in body fluids, muscles and heart can be determined by diluting the blood serum
and aspiration into the flame. Analysis of soft drinks, fruit juices and alcoholic beverages can also be analyzed by
using flame photometry.

Advantages:

Simple quantitative analytical test based on the flame analysis.

Inexpensive.
The determination of elements such as alkali and alkaline earth metals is performed easily with most reliable and
convenient methods.
Quite quick, convenient, and selective and sensitive to even parts per million (ppm) to parts per billion (ppb)
range.

Disadvantages:

Moreover the flame photometer has a wide range of applications in the analytical chemistry, it possess many
disadvantages which are explained below:

The concentration of the metal ion in the solution cannot be measured accurately..
 A standard solution with known molarities is required for determining the concentration of the ions which will
corresponds to the emission spectra.
It is difficult to obtain the accurate results of ions with higher concentration.
The information about the molecular structure of the compound present in the sample solution cannot be
determined.
The elements such as carbon, hydrogen and halides cannot be detected due to its non radiating nature

Unit 4

what is paper?describe one method of manufacture of pulp from wood

pdf

what are the raw materials of portland cement

Portland cement is the most common type of cement in general use around the world as a basic ingredient
of concrete, mortar, stucco, and non-speciality grout. It was developed from other types of hydraulic lime in England in the
mid 19th century and usually originates fromlimestone. It is a fine powder produced by heating limestone and clay minerals
in a kiln to form clinker, grinding the clinker, and adding small amounts of other materials[clarification needed]. Several types of
Portland cement are available. The most common, called ordinary Portland cement (OPC), is grey in color, but white
Portland cement is also available.

Portland cement is caustic, so it can cause chemical burns. The powder can cause irritation or, with severe exposure, lung
cancer and can contain some hazardous components such as crystalline silica and hexavalent chromium. Environmental
concerns are the high energy consumption required to mine, manufacture, and transport the cement and the related air
pollution, including the release of greenhouse gases (e.g., carbon dioxide), dioxin, NOx, SO2, and particulates.

The low cost and widespread availability of the limestone, shales, and other naturally occurring materials used in Portland
cement make it one of the lowest-cost materials widely used over the last century throughout the world. Concrete produced
from Portland cement is one of the most versatile construction materials available in the world

Hydration, Setting and Hardening of

Portland Cement
1. Hydration
 2. Setting and Hardening

1. Hydration
Mechanism

Triealcium silicate hydrates rapidly and forms earlier strength and earlier heat of hydration.
Tricalcium silicate is formed in a kiln when the charge contains an abundance of lime, and
hence the greater amount of CaO in the reaction.

Dicalcium silicate hardrates slowly and is responsible for strength increase in concrete at
later ages. The heat of hydration is liberated slowly. More dicalcium silicate is formed when the
raw materials contain less lime.

Tricalcium aluminate hydrates rapidly and liberates a large amount of heat. If this reaction
was not controlled, concrete would set so rapidly (flash set) that it could not be used in modern
construction.

Ways to avoid flash set

A small amount of gypsum (CaSO42H2O) intergrounding with the cement clinker retards
the hydration reaction of tricalcium aluminate so that the calcium silicates can set firstly.
 Mechanism of Modifying Setting Time by Gypsum

The protecting layer, which is formed by wrapping up the clinker by calcium

sulfoaluminate hydrate needle crystal, hinders the entry of water, slows down hydration and
stops flash setting. Thus the gypsum can modify the setting time.

Not Too Much of Gypsum

After hydration, tricalcium aluminate will react principally with sodium and magnesium
sulfate, found in soil and water, which causes the concrete to disintegrate. Moderate sulfate-
resisting cement limits the percentage of tricalcium aluminate to 8 percent. This compound is
limited to 5 percent in sulfate-resisting cement.

In full hydration hydrate produced by clinker hydration is as following: Calcium silicate

hydrate gel (70%); Calcium hydroxide (20%); Calcium aluminate hydrate; Calcium ferrite
hydrate; Ettringite.

Fig.3.2.2 Degree of Hydration

 2. Setting and Hardening
Definition

Setting Process: The process of losing plasticity and becoming dense of the paste, which is
formed by mixing the cement and water.

Hardening Process: The process of forming hardening cement paste by the paste, which
loses plasticity and its strength increases with time.

Process

Factors

Factors such as: fineness and types of cement, blend of gypsum, age, temperature and
humidity which influence setting and hardening of Portland cement.

Fig.3.2.3 Factors influencing Setting and Hardening