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Page 1

Chemical Bonding

Introduction

Where it fits: Perhaps the chapter that will solve almost all doubts and concept related questions in Chemistry (Trust me I am not exaggerating). It is of utmost importance to understand this chapter and all the concepts in great details. Motivation: There are a lot of elements but very few of them exist in their native form (inert gases). Most of the elements exist as compounds, as the atoms (which are not stable) combine to form more stable molecules. There is some attractive force in the molecules which is called chemical bond. But why and how do the atoms combine and why different compounds have different properties?

Octet Rule

The Octet Rule requires all atoms in a molecule to have 8 valence electrons--either by sharing, losing or gaining electrons--to become stable. For Covalent bonds, atoms tend to share their electrons with each other to satisfy the Octet Rule. It requires 8 electrons because that is the amount of electrons needed to fill a shell (electron configuration); also known as a noble gas configuration. Each atom wants to become as stable as the noble gases that have their outer valence shell filled because noble gases have a charge of 0. Although it is important to remember the "magic number", 8, note that there are many Octet rule exceptions. Example: As you can see from the picture below, Phosphorus has only 5 electrons in its outer shell (bolded in red). Argon has a total of 8 electrons (bolded in red), which satisfies the Octet Rule. Phosphorus needs to gain 3 electrons to fullfill the Octet Rule. It wants to be like Argon who has a full outer valence shell.

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Lewis structures are also known as electron dot structures. The diagrams are named for Gilbert N. Lewis, who described them in his 1916 article entitled The Atom and the

Molecule. Lewis structures depict the bonds between atoms of a molecule as well as any

unbonded electron pairs. You can draw a Lewis dot structure for any covalent molecule or coordination compound. Drawing Lewis structures can be a straightforward process if the proper steps are followed. There are several different strategies to constructing Lewis structures. These instructions outline the Kelter strategy to draw Lewis structures for molecules. Step 1: Find the total number of valence electrons. In this step, add up the total number of valence electrons from all the atoms in the molecule. Step 2: Find the number of electrons needed to make the atoms "happy". An atom is considered "happy" if the atom's outer electron shell is filled. Elements up to period four on the periodic table need eight electrons to fill their outer electron shell. This property is often known as the "octet rule". Step 3: Determine the number of bonds in the molecule. EDUDIGM 1B Panditya Road, Kolkata 29

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Covalent bonds are formed when one electron from each atom forms an electron pair. Step 2 tells how many electrons are needed and Step 1 is how many electrons you have. Subtracting the number in Step 1 from the number in Step 2 gives you the number of electrons needed to complete the octets. Each bond formed requires two electrons, so the number of bonds is half the number of electrons needed, or

Step 4: Choose a central atom. The central atom of a molecule is usually the least electronegative atom or the atom with the highest valence. Hydrogen and halogen atoms tend to appear on the outside of the molecule and are rarely the central atom.

Step 5: Draw a skeletal structure. Connect the atoms to the central atom with a straight line representing a bond between the two atoms. The central atom can have up to four other atoms connected to it. Step 6: Place electrons around outside atoms. Complete the octets around each of the outer atoms. If there are not enough electrons to complete the octets, the skeletal structure from step 5 is incorrect. Try a different arrangement. Step 7: Place remaining electrons around the central atom. Complete the octet for the central atom with the remaining electrons. If there are any bonds left over from Step 3, create double bonds with lone pairs on outside atoms. If there are more than eight electrons on the central atom and the atom is not one of the exceptions to the octet rule, the number of valence atoms in Step 1 may have been counted incorrectly. This will complete the Lewis dot structure for the molecule. Check out Draw a Lewis Structure of Formaldehyde for an example problem using this process.

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The real ambition of the atoms in molecules is to maximize their bonding interactions. There are limitations. One simply cannot keep drawing lines between atoms without justification. Limitation 1: Each bond represents two electrons, there can only be so many bonds based on the number of valence electrons present. Limitation 2: each atom has only a certain number of valence orbitals which it can use while making bonds. Hydrogen only has a 1s orbital available so it's total electron count is limited to 2 ( a single bond). The second period elements (with only 2s + 2p available) are limited to total electron counts of 8. Limitation 3: Geometric constraints arise because the atomic orbitals on atoms have certain directional character (with the exception of "s" orbitals which are spherical). This allows them to bond effectively in only certain ways. This limitation will be expounded upon later, but suffice it to say that two carbon atoms bonded in the gas phase (C2) cannot exhibit a bond order of 4 because all three 2p orbitals cannot localize electron density between the nuclei simultaneously.

Key Points

*Atoms in molecules want to make bonds (within reason), not necessarily attain an octet of electrons. *The number of available orbitals and electrons gives rise to an "octet" rule for 2nd period elements which maximize their bonding interactions when the attain a total electron count of 8.

We have already seen and are quite comfortable with the fact that hydrogen cannot handle anything but a total electron count of 2. This should open your eyes to the reality underlying Lewis Structures! This is the first example of a violation to the socalled octet rule. What about a substance like BH3? The best Lewis structure is depicted below. .

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. Each hydrogen exhibits it's maximum total electron count (2) and not surprisingly it's maximum number of bonds. The boron atom in BH3, on the other hand, has only 6 total electrons. This apparent problem is not a problem when one considers the principles discussed above AND the fact that the real "rule" is that boron cannot EXCEED an octet of electrons. Consider BF3 as well. .

. I consider the best Lewis Structure to be the one shown on the left (I), while few would argue that the one on the right (II) is better. The presence of lone pair electrons on each F atom potentially allows additional bonding interactions. The problem with II is the formal charges which imply that electronegative fluorine is losing the electron density tug-of-war with boron! (The electronegativity difference between these two elements is similar to the difference between Na and Cl, a strong electrolyte!) Another case where the "octet rule" must be violated are reactive species with an odd number of valence electrons. A perfect example is nitrogen monoxide (nitric oxide), NO. This species has 11 valence electrons. There is absolutely NO way to have all the electrons pair up and one of the atoms must have an odd total electron count as well. The best Lewis structure maximizes the number of bonds but does not violate the true octet rule: neither 2nd period atom exceeds an octet! . . The last type of "apparent" exception to the octet rule occurs when an element of the 3rd period or higher is the central atom in a molecule or molecular ion AND it is bonded to electronegative substituents such as O, F, Cl, Br. Examples: XeF4, SF6, PCl5, [SeBr6]2-, IO4-, ClO4- etc...

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VSEPR Theory

The VSEPR theory, proposed by R.J.Gillespie and R.S. Nyholmm in 1957, is based on the repulsions between the electron-pairs in the valence-shell of the atoms in the molecule. According to VSEPR Theory Definition, it was developed to predict the shapes of the molecules in which the atoms are bonded together with single bonds only. VSEPR Theory is abbreviated as Valence Shell Electron Pair Repulsion Theory. In this article, we will learn the main postulates of VSEPR theory.

Given below are some of the postulates of VSEPR Theory.

The shape of the molecule is determined by both the total number of electron pairs (bonding and non-bonding) around the molecules central atom and the orientation of these electron pairs in the space around the central atom. In order to minimize the repulsion forces between them, electron pairs around the molecules central atom, tend to stay as far away from each other as possible. Electron pairs around the molecule's central atom can be shared or can be lone pairs. The 'shared pairs' of electrons are also called bond pairs of electrons. The presence of lone pair(s) of electrons on the central atom causes some distortions in the expected regular shape of the molecule. The strength of repulsions between different electron pairs follows the order:

Lone pair - Lone pair > Lone pair - Shared pair > Shared pair - Shared pair.

To use VSEPR theory for predicting the shapes of molecules, the number of electron pairs (both, shared and lone pairs) is simply counted. This is illustrated by taking a typical molecule of the type ABn. 'A' is the central atom, 'B' atoms are bonded to 'A' by single covalent bonds (single electron pair bonds), and 'n' is the number of 'B' atoms bonded to one atom of 'A'. In a molecule having two bond pairs of electrons around its central atom, the bond pairs are located on the opposite sides (at an angle of 180o) so that the repulsion between them is minimum. Such molecules are therefore linear. Some molecules, which show linear geometry are: BeF2 (beryllium fluoride), BeCl2 (beryllium chloride), BeH2 (beryllium hydride), ZnCl2 (zinc chloride), and HgCl2 (mercuric chloride).

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In a molecule having three bond pairs of electrons around its central atom, the electron pairs form an equilateral triangular arrangement around the central atom. These molecules have trigonal planar (or triangularplanar) shape and the three bond pairs are at 120C with respect of each other. In a molecule of the type AB3, the three bond pairs of electrons are located around A in a triangular arrangement and the molecule AB3, has a triangular planar geometry. Some molecules that show triangular planar geometry are BCl3, BF3, etc.

Molecule having four bond pairs of electrons around the central atom, arrange their electrons tetrahedrally. These molecules have tetrahedral shapes and the four bond pairs are at an angle of 109.

Five bond pairs orient themselves around the central atom in a trigonal bipyramidal way. A molecule having five bond pairs around its central atom has a triangular bipyramidal shape. Three bond pairs are arranged in an equatorial triangular plane and are oriented at an angle of 120 with respect to each other. The other two bond pairs are opposite to each other, and at right angles to the triangular plane formed by the three bond pairs. Some other molecules, which show trigonal bipyramidal geometry are; PCl5, PF5, SbCl5. For example in a molecule of the type AB5, the five bond pairs are distributed in a trigonal bipyramidal around the central atom 'A'. Therefore, the molecules of the type AB5 are trigonal bipyramidal in shape.

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AB5, five bond pairs are oriented around A in a trigonal bipyramidal shape.Similarly,PCl5 also has a trigonal bipyramidal shape.

Six bond pairs in a molecule are distributed octahedrally around the central atom. A molecule having six bond pairs around its central atom has an octahedral shape. In a molecule of the type AB6, the six 'B' atoms are placed octahedrally around 'A'. Thus, the molecules of the type AB6 are octahedral. The molecule SF6 has an octahedral geometry.

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VSEPR Table

No. of Electron Pair No. of lone VSEPR Example Pairs Notation Molecular Geometry Formula Image

linear (180o)

AX2

BeH2

linear 3 trigonal (120o) trigonal planar 1 AX2E SO2 planar 0 AX3 BF3

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AX4E

SF4

square planar

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Given below is an example based on VSEPR Theory. Example : Predict the shapes of the following molecules using the valence shell electron pair repulsion (VSEPR) theory. AsF5, HgBr2. Solution: According to the VSEPR theory, the electron pairs present is the valence-shell of the central atom/ion arrange themselves in the space around it so as to keep them as far as possible from each other, so as to minimize the electrostatic repulsions.

As has five electrons in its outermost orbit. Due to sharing of 5 electrons from 5F-atoms, there are in all 5 electron pairs. These are distributed in space to form a trigonal bipyramid as shown here.

Hg has only two electrons in its outermost orbit and sharing these electrons with two Br gives 2 pairs of electrons around Hg. This gives a linear structure to (electron pairs are positioned at 180)

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The VSEPR theory is simple yet powerful. Nevertheless, like any simplified model, it has its limitations. First, although it predicts that the bond angle in H2O is less than the tetrahedral angle, it does not make any attempt to predict the magnitude of the decrease. Second, the theory makes no predictions about the lengths of the bonds, which is another aspect of the shape of a molecule. Third, it ascribes the entire criterion of shape to electrostatic repulsions between bonding pairs, when in fact there are numerous contributions to the total energy of a molecule, and electrostatic effects are not necessarily the dominant ones. Fourth, the theory relies on some vague concepts, such as the difference in repelling effects of lone pairs and bonding pairs. There also are some species for which VSEPR theory fails. Nevertheless, despite these limitations and uncertainties, VSEPR theory is a useful rule of thumb and can be used with reasonable confidence for numerous species. To Sum Up: (i) It does not explain the shapes of the molecules having very polar e.g. angular (ii) (iii) (iv) It does not explain the shapes of the molecules or ions which are extensive by delocalized -electron system It does not explain the shapes of some molecules which have an inert pair of electrons. It does not explain the shapes of certain compounds of transitional metals e.g. the shape of the compound electronic configuration of the central atom, is square planar and not tetrahedral as predicted b this theory should have same structure but is linear while is

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The valence bond theory was proposed by Heitler and London to explain the formation of covalent bond quantitatively using quantum mechanics. Later on, Linus Pauling improved this theory by introducing the concept of hybridization. The main postulates of this theory are as follows: * A covalent bond is formed by the overlapping of two half filled valence atomic orbitals of two different atoms. * The electrons in the overlapping orbitals get paired and confined between the nuclei of two atoms. * The electron density between two bonded atoms increases due to overlapping. This confers stability to the molecule. * Greater the extent of overlapping, stronger is the bond formed. * The direction of the covalent bond is along the region of overlapping of the atomic orbitals i.e., covalent bond is directional. * There are two types of covalent bonds based on the pattern of overlapping as follows: (i) -bond: The covalent bond formed due to overlapping of atomic orbital along the inter nucleus axis is called -bond. It is a stronger bond and cylindrically symmetrical. Depending on the types of orbitals overlapping, the -bond is divided into following types: s-s bond:

p-p bond:

s-p bond:

(ii) -bond: The covalent bond formed by sidewise overlapping of atomic orbitals is called - bond. In this bond, the electron density is present above and below the inter nuclear axis. It is relatively a weaker bond since the electrons are not strongly attracted by the nuclei of bonding atoms.

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Note: The 's' orbitals can only form -bonds, whereas the p, d & f orbitals can form both and -bonds.

Examples

Example : H2 molecule: * The electronic configuration of hydrogen atom in the ground state is 1s1. * In the formation of hydrogen molecule, two half filled 1s orbitals of hydrogen atoms overlap along the inter-nuclear axis and thus by forming a s-sbond.

Example :Cl2 molecule: * The electronic [Ne]3s2 3px2 3py2 3pz1. configuration of Cl atom in the ground state is

* The two half filled 3pz atomic orbitals of two chlorine atoms overlap along the inter-nuclear axis and thus by forming a p-p bond.

Example : HCl molecule: * In the ground state, the electronic configuration of hydrogen atom is 1s1. * And the ground state electronic configuration of Cl atom is [Ne]3s2 3px2 3py2 3pz1. * The half filled 1s orbital of hydrogen overlap with the half filled 3p z atomic orbital of chlorine atom along the inter-nuclear axis to form a s-p bond.

Example : O2 molecule:

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* The electronic configuration of O in the ground state is [He] 2s2 2px2 2py1 2pz1. * The half filled 2py orbitals of two oxygen atoms overlap along the inter-nuclear axis and form p-p bond. * The remaining half filled 2pz orbitals overlap laterally to form a p-p bond. * Thus a double bond (one p-p and one p-p) is formed between two oxygen atoms.

Example : N2 molecule: * The ground state electronic configuration of N is [He] 2s2 2px1 2py1 2pz1. * A p-p bond is formed between two nitrogen atoms due to overlapping of half filled 2px atomic orbitals along the inter-nuclear axis. * The remaining half filled 2py and 2pz orbitals form two p-p bonds due to lateral overlapping. Thus a triple bond (one and two) is formed between two nitrogen atoms.

However the old version of valence bond theory is limited to diatomic molecules only. It could not explain the structures and bond angles of molecules with more than three atoms. E.g. It could not explain the structures and bond angles of H2O, NH3 etc., However, in order to explain the structures and bond angles of molecules, Linus Pauling modified the valence bond theory using hybridization concept.

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Hybridization

What is hybridization?

The intermixing of two or more pure atomic orbitals of an atom with almost same energy to give same number of identical and degenerate new type of orbitals is known as hybridization. The new orbitals formed are also known as hybrid orbitals.

What is intermixing?

The intermixing or hybridization of atomic orbitals is a mathematical concept based on quantum mechanics. During this process, the wave functions, of atomic orbitals of same atom are combined to give new wave functions corresponding to hybrid orbitals.

* The atomic orbitals of same atom with almost same energy can only participate in the hybridization. * The full filled or half filled or even empty orbitals can undergo hybridization provided they have almost equal energy.

No! The hybridization is the mixing of orbitals of same atom only. The combination of orbitals belonging to different atoms is called bonding.

* The new orbitals that are formed due to intermixing of atomic orbitals are also known as hybrid orbitals, which have mixed characteristics of atomic orbitals. * The shapes of hybrid orbitals are identical. Usually they have one big lobe associated with a small lobe on the other side. * The hybrid orbitals are degenerate i.e., they are associated with same energy. How many hybrid orbitals are formed? * The number of hybrid orbitals formed is equal to the number of pure atomic orbitals undergoing hybridization. E.g. If three atomic orbitals intermix with each other, the number of hybrid orbitals formed will be equal to 3.

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* The hybrid orbitals are filled with those electrons which were present in the pure atomic orbitals forming them. * The filling up of electrons in them follows Pauli's exclusion principle and Hund's rule. What is the use of hybrid orbitals? * The hybrid orbitals participate in the bond formation with other atoms. Why atomic orbitals in a given atom undergo hybridization? * The hybrid orbitals are oriented in space so as to minimize repulsions between them. This explains why the atomic orbitals undergo hybridization before bond formation. The reason for hybridization is to minimize the repulsions between the bonds that are going to be formed by the atoms by using hybrid orbitals. Remember that the hybridization is the process that occurs before bond formation.

And finally:

* The bond angles in the molecule are equal to or almost equal to the angles between the hybrid orbitals forming the bonds. The shape of the molecule is determined by the type of hybridization, number of bonds formed by them and the number of lone pairs.

Types of Hybridization

During hybridization, the atomic orbitals with different characteristics are mixed with each other. Hence there is no meaning of hybridization between same type of orbitals i.e., mixing of two 's' orbitals or two 'p' orbitals is not called hybridization. However orbital of 's' type can can mix with the orbitals of 'p' type or of 'd' type. Based on the type and number of orbitals, the hybridization can be subdivided into following types. sp HYBRIDIZATION * Intermixing of one 's' and one 'p' orbitals of almost equal energy to give two identical and degenerate hybrid orbitals is called 'sp' hybridization. * These sp-hybrid orbitals are arranged linearly at by making 180o of angle. * They possess 50% 's' and 50% 'p' character.

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Example : Beryllium Chloride (BeCl2): * The electronic configuration of 'Be' in ground state is 1s2 2s2. Since there are no unpaired electrons, it undergoes excitation by promoting one of its 2s electron into empty 2p orbital. Thus in the excited state, the electronic configuration of Be is 1s2 2s1 2p1. If the beryllium atom forms bonds using these pure orbitals, the molecule might be angular. However the observed shape of BeCl2 is linear. To account for this, following sp hybridization was proposed. * In the excited state, the beryllium atom undergoes 'sp' hybridization by mixing a 2s and one 2p orbitals. Thus two half filled 'sp' hybrid orbitals are formed, which are arranged linearly.

* These half filled sp-orbitals form two bonds with two 'Cl' atoms. * Thus BeCl2 is linear in shape with the bond angle of 180o.

Example : Acetylene (C2H2): * The ground state electronic configuration of 'C' is 1s2 2s2 2px12py1. There are only two unpaired electrons in the ground state. However, the valency of carbon is four i.e., it forms 4 bonds. In order to form four bonds, there must be four unpaired electrons. Hence carbon promotes one of its 2s electron into the empty 2p z orbital in the excited state. 1s2 Thus in the excited 2s1 2px12py12pz1. state, the electronic configuration of carbon is

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* Each carbon atom undergoes 'sp' hybridization by using a 2s and one 2p orbitals in the excited state to give two half filled 'sp' orbitals, which are arranged linearly. * The two carbon atoms form a sp-sp bond with each other by using sp-orbitals. However there are also two unhybridized p orbitals i.e., 2py and 2pz on each carbon atom which are perpendicular to the sp hybrid orbitals. These orbitals form two pp bonds between the two carbon atoms. Thus a triple bond (including one sp-sp bond & two p-p bonds ) is formed between carbon atoms. * Each carbon also forms a sp-s bond with the hydrogen atom. * Thus acetylene molecule is linear with 180o of bond angle.

sp2 HYBRIDIZATION * Intermixing of one 's' and two 'p' orbitals of almost equal energy to give three identical and degenerate hybrid orbitals is known as sp2 hybridization. * The three sp2 hybrid orbitals are oriented in trigonal planar symmetry at angles of 120o to each other. * The sp2 hybrid orbitals have 33.3% 's' character and 66.6% 'p' character.

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Example : Boron trichloride (BCl3): * The electronic configuration of 'B' in ground state is 1s2 2s2 2p1 with only one unpaired electron. Since the formation of three bonds with chlorine atoms require three unpaired electrons, there is promotion of one of 2s electron into the 2p sublevel by absorbing energy. Thus Boron atom gets electronic configuration: 1s2 2s2 2px12py1. However to account for the trigonal planar shape of this BCl3 molecule, sp2 hybridization before bond formation was put forwarded. * In the excited state, Boron undergoes sp2 hybridization by using a 2s and two 2p orbitals to give three half filled sp2 hybrid orbitals which are oriented in trigonal planar symmetry. * Boron forms three sp-p bonds with three chlorine atoms by using its half filled sp2 hybrid orbitals. Each chlorine atom uses it's half filled p-orbital for the -bond formation. * Thus the shape of BCl3 is trigonal planar with bond angles equal to 120o.

Example : Ethylene (C2H4): * During the formation of ethylene molecule, each carbon atom undergoes hybridization in its excited state by mixing 2s and two 2p orbitals to give three half filled sp2 hybrid orbitals oriented in trigonal planar symmetry. sp2 EDUDIGM 1B Panditya Road, Kolkata 29

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There is also one half filled unhybridized 2pz orbital on each carbon perpedicular to the plane of sp2 hybrid orbitals.

* The carbon atoms form a sp2-sp2 bond with each other by using sp2 hybrid orbitals. A p-p bond is also formed between them due to lateral overlapping of unhybridized 2pz orbitals. Thus there is a double bond (sp2-sp2 & p-p) between two carbon atoms. * Each carbon atom also forms two sp2-s bonds with two hydrogen atoms. * Thus ethylene molecule is planar with HCH & HCC bond angles equal to 120o. * All the atoms are present in one plane.

sp3 HYBRIDIZATION * In sp3 hybridization, one 's' and three 'p' orbitals of almost equal energy intermix to give four identical and degenerate hybrid orbitals. * These four sp3 hybrid orbitals are oriented in tetrahedral symmetry with 109o28' angle with each other. * The sp3 hybrid orbitals have 25% s character and 75% 'p' character.

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* During the formation of methane molecule, the carbon atom undergoes hybridization in the excited state by mixing one 2s and three 2p orbitals to furnish four half filled sp3 hybrid orbitals, which are oriented in tetrahedral symmetry in space around the carbon atom. sp3 * Each of these sp3 hybrid orbitals forms a sp3-s bond with one hydrogen atom. Thus carbon forms four sp3-s bonds with four hydrogen atoms. * Methane molecule is tetrahedral in shape with 109o28' bond angle.

Example : Ethane (C2H6): * Just like in methane molecule, each carbon atom undergoes sp3 hybridization in the excited state to give four sp3 hybrid orbitals in tetrahedral geometry. sp3 * The two carbon atoms form a sp3-sp3 bond with each other due to overlapping of hybrid orbitals along the inter-nuclear axis. Each carbon atom also forms three sp3-s bonds with hydrogen atoms. * Thus there is tetrahedral symmetry around each carbon with HCH & HCC bond angles equal to 109o28'.

Example : Ammonia (NH3) * The ground state electronic configuration of nitrogen atom is: 1s2 2s2 2px12py12pz1. Since there are three unpaired electrons in the 2p sublevel, the nitrogen atom can form three bonds with three hydrogen atoms. This will give ammonia molecule with 90o of bond angles. However, the bond angles are reported to be 107o48'. * Therefore, it was proposed that, the Nitrogen atom undergoes sp3 hybridization of a 2s and three 2p orbitals to give four sp3 orbitals, which are arranged in tetrahedral

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symmetry. It is clear that this arrangement will give more stability to the molecule due to minimization of repulsions. Among them three are half filled and one is full filled.

* Nitrogen atom forms 3 sp3-s bonds with three hydrogen atoms by using three half filled sp3 hybrid orbitals. There is also a lone pair on nitrogen atom belonging to the full filled sp3 hybrid orbital. It occupied more space than the bond pairs. * However, the HNH bond angle is not equal to normal tetrahedral angle: 109o28'. The reported bond angle is 107o48'. The observed decrease in the bond angle is due to the repulsion caused by lone pair over the bond pairs. That is why, ammonia molecule is trigonal pyramidal in shape with a lone pair on nitrogen atom.

Example : Water molecule (H2O) * The electronic configuration of oxygen is 1s2 2s2 2px22py12pz1. There are two unpaired electrons in oxygen atom, which may form bonds with hydrogen atoms. However the the bond angles in the resulting molecule should be equal to 90o. sp3 sp3 The experimental bond angles reported were equal to 104o28'. To account this, hybridization before the bond formation was proposed.

* During the formation of water molecule, the oxygen atom undergoes hybridization by mixing a 2s and three 2p orbitals to furnish four sp 3 hybrid orbitals oriented in tetrahedral geometry. Among them, two are half filled and the remaining two are completely filled.

* Now the oxygen atom forms two sp3-s bonds with hydrogen atoms by using half filled hybrid orbitals.

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* The reported bond angle is 104o28' instead of regular tetrahedral angle: 109o28'. It is again due to repulsions caused by two lone pairs on the bond pairs. Thus water molecule gets angular shape (V shape).

sp3d HYBRIDIZATION * In sp3d hybridization, one 's', three 'p' and one 'd' orbitals of almost equal energy intermix to give five identical and degenerate hybrid orbitals, which are arranged in trigonal bipyramidal symmetry. Among them, three are arranged in trigonal plane and the remaining two orbitals are present above and below the trigonal plane at right angles. * The sp3d hybrid orbitals have 20% 's', 60% 'p' and 20% 'd' characters.

Example : Phosphorus pentachloride(PCl5) * The ground state 1s2 2s22p6 3s23px13py13pz1. electronic configuration of phosphorus atom is:

* The formation of PCl5 molecule requires 5 unpaired electrons. Hence the phosphorus atom undergoes excitation to promote one electron from 3s orbital to one of empty 3d orbital. 1s2 * Thus the electronic configuration 2s22p6 3s23px13py13pz1 3d1. of 'P' in the excited state is

* In the excited state, intermixing of a 3s, three 3p and one 3d orbitals to give five half filled sp3d hybrid orbitals, which are arranged in trigonal bipyramidal symmetry. i.e., Three orbitals are arranged in trigonal planar symmetry, whereas the remaining two are arranged perpendicularly above and below this plane. EDUDIGM 1B Panditya Road, Kolkata 29

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* By using these half filled sp3d orbitals, phosphorous forms five sp3d-p bonds with chlorine atoms. Each chlorine atom makes use of half filled 3pzorbital for the bond formation. * The shape of PCl5 molecule is trigonal bipyramidal with 120o and 90o of Cl - P - Cl bond angles.

sp3d2 HYBRIDIZATION * Intermixing of one 's', three 'p' and two 'd' orbitals of almost same energy by giving six identical and degenerate hybrid orbitals is called sp3d2hybridization. * These six sp3d2 orbitals are arranged in octahedral symmetry by making 90o angles to each other. This arrangement can be visualized as four orbitals arranged in a square plane and the remaining two are oriented above and below this plane perpendicularly.

Example : Sulfur hexa flouride (SF6): * The electronic configuration of 'S' in ground state is 1s2 2s22p6 3s23px23py13pz1. * In SF6 molecule, there are six bonds formed by sulfur atom. Hence there must be 6 unpaired electrons. However there are only 2 unpaired electrons in the ground state of sulfur. Hence it promotes two electrons into two of the 3d orbitals (one from 3s and one from 3px). 1s2 * Thus the electronic configuration 2s22p6 3s13px13py13pz13d2. of 'S' in its 2nd excited state is

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* In the second excited state, sulfur under goes sp3d2 hybridization by mixing a 3s, three 3p and two 3d orbitals. Thus formed six half filled sp3d2hybrid orbitals are arranged in octahedral symmetry. Sulfur atom forms six sp3d2-p bonds with 6 fluorine atoms by using these sp3d2 orbitals. Each fluorine atom uses is half-filled 2pz orbitals for the bond formation. SF6 is octahedral in shape with bond angles equal to 90o.

sp3d3 HYBRIDIZATION * In sp3d3 hybridization, one 's', three 'p' and three 'd' orbitals of almost same energy intermix to give seven sp3d3 hybrid orbitals, which are oriented in pentagonal bipyramidal symmetry. * Five among the sp3d3 orbitals are arranged in a pentagonal plane by making 72o of angles. The remaining are arranged perpendicularly above and below this pentagonal plane.

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* The electronic configuration of Iodine atom in the ground state is: [Kr]4d105s25p5. Since the formation of IF7 requires 7 unpaired electrons, the iodine atom promotes three of its electrons (one from 5s orbital and two from 5p sublevel) into empty 5d orbitals. This state is referred to as third excited state. * The electronic configuration of Iodine in the third excited state can be written as: [Kr]4d105s15p35d3.

In the third excited state, iodine atom undergoes sp3d3 hybridization to give 7 half filled sp3d3 hybrid orbitals in pentagonal bipyramidal symmetry. These will form 7 sp3d3-p bonds with fluorine atoms. Thus the shape of IF7 is pentagonal bipyramidal. The F-I-F bond angles in the pentagonal plane are equal to 72o, whereas two fluorine are present perpendicularly to the pentagonal plane above and below.

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Introduction

When carbon (C) reacts with oxygen (O), carbon dioxide is produced. Can you write the chemical equation for the same? The chemical equation for the reaction is: In this reaction, one atom of carbon combines with one molecule or two atoms of oxygen to form one molecule of carbon dioxide. We can also say that in this chemical reaction, 12 u of carbon atoms combine with 32 u of oxygen molecules to give 44 u of carbon dioxide. Hence, the quantity of substances can be represented in terms of the number of molecules or its mass. However, a chemical equation only indicates the number of atoms or molecules taking part in the chemical reaction. Therefore, it is easier to represent the quantity of a substance by the number of atoms or molecules rather than its mass. In order to do the same, a new term mole was introduced.

Do You Know? The word mole is derived from the Latin word moles meaning heap or pile. It was first introduced by Wilhelm Ostwald in 1896, but was accepted universally in 1967 as a way of indicating the number of atoms or molecules in a sample.

The molecules of an element are composed of identical atoms. For example, an oxygen molecule (O2) consists of two oxygen atoms, and a nitrogen molecule (N2) consists of two nitrogen atoms. N2 and O2 are called diatomic molecules. Thus, the atomicity of nitrogen and oxygen is two. When three atoms of oxygen combine, a molecule of ozone (O3) is formed. Here, the atomicity of oxygen is three. Can you define atomicity? The number of atoms constituting a molecule is known as its atomicity. The atomicity of some common elements is given below.

Non-metal Helium

Atomicity Monoatomic

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Neon Argon Oxygen Hydrogen Nitrogen Chlorine Fluorine Phosphorus Sulphur Tetra-atomic Polyatomic(8 atoms per molecule) Diatomic

One mole of a substance (atoms, molecules, ions, or particles) is that quantity in number having a mass equal to its atomic or molecular mass in grams. One mole of any substance contains 6.022 1023 particles (atoms, molecules, or ions). This means that one mole atom of any substance contains 6.022 1023 atoms. Similarly, one mole molecule of any substance contains 6.022 1023 molecules and one mole ion of any substance contains 6.022 1023 ions. Hence, the mass of a particular substance is fixed.

The number 6.022 1023 is an experimentally obtained value and is known as Avogadros number or Avogadro constant (represented by No). It is named after the Italian scientist, Amedeo Avogadro.

Thus, 1 mole of oxygen atoms (O) = 6.022 1023 oxygen atoms 1 mole of oxygen molecules (O2) = 6.022 1023 oxygen molecules 1 mole atoms of an element has a mass equal to the gram atomic mass of that element. Hence, the mass of 1 mole molecules is equal to its molecular mass in grams. The atomic mass of an element is the mass of its atom in atomic mass units (u). By taking the same numerical value of atomic mass and changing the units from u to g, the mass of 1 mole atoms of that element is obtained. The mass of one mole of atoms is known as the molar mass of atoms, gram atomic mass, or gram atoms. For example, the atomic mass of nitrogen is 14 u and the gram atomic mass of nitrogen is 14 g.

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Similarly, the molecular mass of a substance gives the mass of a molecule of that substance in atomic mass units (u). Therefore, as discussed earlier, by taking the same numerical value of molecular mass and by changing its units from u to g, the mass of one mole molecules of that substance can be obtained. Therefore, the mass of one mole molecules of any substance is equal to the gram molecular mass of that substance. For example, 12 u of carbon contains only 1 atom of carbon; and 12 g carbon contains 1 mole atoms of carbon i.e., 6.022 1023 number of carbon atoms. Similarly, the molecular mass of oxygen (O2) is 32 u. Thus, its gram molecular mass is 32 g. Thus, 32 g of O2 contains 1 mole molecules of O2 i.e., 6.022 1023 number of molecules of oxygen.

Relative Atomic Mass, Relative Molecular Mass, Gram Molecular Volume and Mole

Initially, hydrogen atom was chosen as a standard unit and masses of other atoms were compared with it. However, this created a problem as hydrogen had 3 isotopes. Relative mass is obtained by relating mass of an atom of an element or a molecule of a compound to the mass of lightest atom.

One twelfth mass of an isotope of a carbon atom is called atomic mass unit. Atomic mass unit is only number and it has no units. On the basis of above unit, the atomic mass of carbon atom is 12 amu.

Definition with respect to hydrogen:

It is the ratio of mass of one atom of an element to the mass of an atom of hydrogen taken as unity.

It is the ratio of mass of one atom of an element to 1/12th mass of an atom of carbon.

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Definition with respect to hydrogen: It is the ratio of mass of one molecule of a substance to the mass of an atom of hydrogen taken as unity. Definition with respect to carbon: It is the ratio of mass of one atom of an element to 1/12th mass of an atom of carbon.

The volume occupied by 1 gram molecule of a dry gas at S.T.P is called gram molecular volume. The experimental value of 1 gram molecular volume of a gas is 22.4 litres at S.T.P. The relationship between the mole, Avogadros number, and mass is summarised as follows:

1. It helps in determination of atomicity of gases, which occur as elements. The number of atoms present in one molecule of an element is called its atomicity. Example : Elements having one atom in their molecules such as helium and neon are called monatomic while elements having two atoms in their molecules such as hydrogen and oxygen are called diatomic. EDUDIGM 1B Panditya Road, Kolkata 29

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Elements having more than three atoms in their molecules such as sulphur molecule and carbon molecule are called polyatomic. 2. Explaining Gay lussacs law 3. Determination of relation between gram molecular mass and gram molecular volume The mass of one mole molecules of any substance is equal to the gram molecular mass of that substance. The volume occupied by 1 gram molecule of a dry gas at S.T.P is called gram molecular volume. The experimental value of 1 gram molecular volume of a gas is 22.4 litres at S.T.P. On applying Avogadros law, we obtain Gram molecular volume of gas = Gram molecular mass / density of gas at S.T.P Let us solve a numerical based on this concept. Example : Calculation of gram molecular volume of hydrogen Mass of hydrogen = 2.016g Density of hydrogen = 0.09g/ We know that, Gram molecular volume of gas = Gram molecular mass / density of gas at S.T.P Therefore, Gram molecular volume of hydrogen = 2.016 g /0.09 g/ = 22.4 at S.T.P

4. Relation between relative molecular mass {RMM} and vapour density{VD} Relative molecular mass is the ratio of mass of one molecule of a substance to the mass of an atom of hydrogen taken as unity. Vapour density is the ratio of certain mass of a gas or vapour to the mass of same volume. On applying Avogadros law, we obtain RMM = 2 VD Let us solve a numerical based on this concept.

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Stoichiometry Example : Calculation of relative molecular mass of phosphorous Vapour density of phosphorous = 23 We know, RMM = 2 VD Therefore, RMM of phosphorous = 2 23 = 46 amu 5. Determination of molecular formula of a gas

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Molecular formula gives the actual number of atoms of the different elements present in one molecule of a compound. Example :

Hence, the mole concept can provide us with the following information. 6. If one mole of a substance (atoms, molecules, or ions) is present, then the number of elementary particles present in that substance is equal to 6.022 1023. 7. The mass of one mole of a substance (i.e., atoms, molecules, or ions) is equal to its molar mass. 8. While carrying out reactions, scientists required the number of atoms and molecules. This requirement was fulfilled by the use of the mole concept as: 1 mole = 6.022 1023 = Relative mass in grams Do You Know? One mole of gas occupies a volume of 22.4 litres at STP (standard temperature and pressure conditions i.e., 273 K and 1 atm). The volume occupied by 1 mole of gas at STP is called the molar volume of gas.

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The mole conceptcan be used in various calculations. The use of the mole concept can be understood with the help of the following examples.

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Percentage Composition

It refers to the percentage weight of an element present in the formula weight of a chemical composition.

Let us solve a numerical based on this concept. Example : Calculation of percentage composition of sulphur in copper sulphate Solution: Gram molecular weight of copper sulphate = 1(Cu) + 1(S) + 4(O) = 1(64) + 1(32) +4(16) =160 g Gram weight of element sulphur in copper sulphate = 1(S) = 132 = 32 g We know,

Therefore, Percentage composition of copper in copper sulphate = 32/ 160 100 = 20%

Molecular formula is the chemical formula, which represents the actual number of atoms of each element present in one molecule of a compound.

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Stoichiometry Example : Sulphuric acid has molecular formula 1 sulphur atom, and 4 oxygen atoms.

Empirical Formula

Empirical formula is the chemical formula, which shows the simplest whole number ratio between the atoms of various elements in the compound. Example : Sulphuric acid has molecular formula . Therefore,

Let us study this using an example. To determine the empirical formula of iron oxide from the following percentages: Fe = 72.41%, O = 27.59% Atomic weight of Fe = 56 Atomic weight of O = 16 Percentage weight of Fe = 72.41% Percentage weight of O = 27.59% After obtaining this information, divide percentage weights of each element with its atomic weight. Write the answer up till 2 decimal places. This ratio gives the number of moles of each element. Relative number of moles of iron = 72.41 / 56 = 1.29 Relative number of moles of oxygen = 27.59 / 16 = 1.72 Next, divide each ratio of relative number of moles obtained by the smallest ratio. This gives simplest ratio of atoms present in a compound. If the ratios are not whole

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Stoichiometry numbers, then multiply them by the smallest integer so that the ratios are whole numbers. Here, we will divide each ratio by 1.29. Simple ratio of iron = 1.29/1.29 = 1 Simple ratio of oxygen = 1.72/ 1.29 = 1.33

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To make it a whole number, we will multiply them by the smallest integer so that the ratios are whole numbers i.e., 3. Therefore, Simple ratio of iron = 13 = 3 Simple ratio of oxygen = 1.33 3 = 4 Thus, empirical formula of compound = Determination of molecular formula of a compound from its percentage composition Let us study this using an example. To determine the molecular formula from the following percentage compositions such that vapour density of compound is 30: C = 40%, O = 53.33%, and H = 6.67% Atomic weight of C = 12 Atomic weight of O= 16 Atomic weight of hydrogen = 1 Calculate relative number of moles and simple ratio of atoms as explained above. Relative number of moles of carbon = 40 / 12 = 3.33 Relative number of moles of oxygen = 53.33/ 16 = 3.33 Relative number of moles of hydrogen = 6.67/1 = 6.67 Next, divide each ratio of relative number of moles obtained by the smallest ratio. This gives the simplest ratio of atoms present in the compound. If the ratios are not whole EDUDIGM 1B Panditya Road, Kolkata 29

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Stoichiometry numbers, then multiply them by the smallest integer so that the ratios are whole numbers. Here, we will divide each ratio by 3.33. Simple ratio of carbon = 3.33/3.33 = 1 Simple ratio of oxygen = 3.33/3.33 = 1 Simple ratio of hydrogen = 6.67 / 3.33 =3 Thus, empirical formula of compound = Now, empirical formula weight of =1 12+ 2 1 +1 16 = 30 Molecular weight = 2 Vapour density = 2 30 = 60 N = Molecular weight/ Empirical formula weight = 60/30 = 2 Therefore, molecular formula = 2 Empirical formula = =1 (C) + 2(H) +1(O)

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From the above balanced chemical equation, the following information is obtained:

One mole of C3H8(g) reacts with five moles of O2(g) to give three moles of CO2(g) and four moles of H2O(l). One molecule of C3H8(g) reacts with five molecules of O2(g) to give three molecules of CO2(g) and four molecules of H2O(l). 44 g of C3H8(g) reacts with (5 32 = 160) g of O2(g) to give (3 44 = 132) g of CO2 and (4 18 = 72) g of H2O.

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22.4 L of C3H8(g) reacts with (5 22.4) L of O2(g) to give (3 22.4) L of O2 and (4 22.4) L of H2O.

Example : Nitric acid (HNO3) is commercially manufactured by reacting nitrogen dioxide (NO2) with water (H2O). The balanced chemical equation is represented as follows:

Calculate the mass of NO2 required for producing 5 moles of HNO3. Solution: According to the given balanced chemical equation, 3 moles of NO2 will produce 2 moles of HNO3. Therefore, 2 moles of HNO3 require 3 moles of NO2.

moles of NO2

Molar mass of NO2 = (14 + 2 16) g mol1 = 46 g mol1 Thus, required mass of NO2 = (7.5 46) g mol1 = 345 g mol1

Limiting reagent or limiting reactant: Reactant which gets completely consumed when a reaction goes to completion

So called because its concentration limits the amount of the product formed Example : Lead nitrate reacts with sodium iodide to give lead iodide and sodium nitrate in the following manner:

What amount of sodium nitrate is obtained when 30 g of lead nitrate reacts with 30g of sodium iodide? Solution: Molar mass of

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Stoichiometry = 331 g mol1 Molar mass of NaI = (23 + 127) = 150 g mol1

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According to the given equation, 1 mole of Pb(NO3)2 reacts with 2 moles of NaI, i.e., 331 g of Pb(NO3)2 reacts with 300 g of NaI to give PbI2 and NaNO3 Thus, Pb(NO3)2 is the limiting reagent.

Therefore, 30 g of Pb (NO3)2

mole

According to the equation, 0.09 mole of Pb(NO3)2 will give (2 0.09) mole of NaNO3 = 0.18 mole of NaNO3.

Reactions in Solutions

Ways for expressing the concentration of a solution

Mass per cent Example : 4.4 g of oxalic acid is dissolved in 200 mL of a solution. What is the mass per cent of oxalic acid in the solution? (Density of the solution = 1.1 g mL1) Solution: Density of the solution = 1.1 g mL1 So the mass of the solution = (200 mL) (1.1 g mL1) = 220 g Mass of oxalic acid = 4.4 g Therefore, mass per cent of oxalic acid in the solution

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Mole Fraction

If a substance A dissolves in a substance B, then mole fraction of A

Mole fraction of B

Example : A solution is prepared by dissolving 45 g of a substance X (molar mass = 25 g mol1) in 235 g of a substance Y (molar mass = 18 g mol1). Calculate the mole fractions of X and Y.

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Stoichiometry = 0.879

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Molarity:

M1V1 = M2V2 M1 = Molarity of a solution when its volume is V1 M2 = Molarity of the same solution when its volume is V2

Example : 10g of HCl is dissolved in enough water to form 500 mL of the solution. Calculate the molarity of the solution. Solution: Molar mass of HCl = 36.5 g mol1

mol

Therefore, molarity =

= 0.548 M Example : Commercially available concentrated HCl contains 38% HCl by mass. What volume of concentrated HCl is required to make 2.5 L of 0.2 M HCl? (Density of the solution = 1.19 g mL1) Solution: 38% HCl by mass means that 38g of HCl is present in 100 g of the solution.

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Moles of HCl =

= 84.03 mL = 0.08403L

M1V1 = M2V2

Here,

Now, M1V1 = M2V2

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Molality

Number of moles of solute present in 1 kg of solvent

Molality (m) = Example : What is the molality of a solution of glucose in water, which is labelled as 15% (w/w)? Solution: 15% (w/w) solution means that 15 g of glucose is present in 100 g of the solution, i.e., (100 15) g = 85 g of water = 0.085 kg of water

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1. Calculation of the mass of 0.5 moles of N2 gas: The molecular mass of nitrogen is 28 u. Mass = Molar mass Number of moles Mass = 28 g 0.5 = 14 g 2. Calculation of the number of moles and number of molecules present in 18.066 1023 particles of nitrogen: 1 mole = 6.022 1023

Therefore, the number of molesis 3. 1 mole of nitrogen contains 6.022 1023 molecules. Therefore, 3 moles of nitrogen contains = 6.022 1023 3 molecules = 18 1023 molecules Therefore, the number of molecules is 18 1023. 3. Calculation of the molecular weight of lead nitrate (Pb= 207; N= 14; O= 16) Molecular weight of lead nitrate = 1 (Pb) + 2(N) + 6(O) = 1 207 + 2 14 +6 16 = 331 amu Thus, the molecular weight of lead nitrate is 331 amu.

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Stoichiometry 4. Calculation of the volume occupied by 6 g of oxygen gas at S.T.P. Molecular weight of oxygen ( ) = 2 16 = 32 amu ) = 32 g

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Now, 32 g of oxygen will occupy at S.T.P = 22.4 Therefore, 6 g will occupy at S.T.P = 22.4 6 / 32 = 4.2 Example : What number of moles contains 3.011 1023 molecules of glucose? Solution: 1 mole of glucose is equivalent to 6.022 1023 molecules of glucose. Hence, 3.011 1023 molecules of glucose will be present in

mol = 0.5 mol (of glucose) Thus, 0.5 mole of glucose contains 3.011 1023 molecules of glucose. Example : What is the mass of a mole of fluorine molecule? Solution: 1 mole of fluorine molecule contains 6.022 1023 molecules and weighs 38 g.

Example : One million silver atoms weigh 1.79 x 1016 g. Calculate the gram atomic mass of silver. Solution: Number of silver atoms = 1 million = 1 x 106 Mass of one million Ag atoms = 1.79 x 1016 g

= 107.8 g Gram atomic mass of silver is equal to the mass of 6.023 x 1023 atoms of silver. So, the gram atomic mass of silver is 107.8 g. EDUDIGM 1B Panditya Road, Kolkata 29

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Example : A sample of gaseous substance weighing 0.5 g occupies a volume of 1.12 litre under NTP conditions. Calculate the molar mass of the substance. Solution: 1 mole of any gaseous substance at NTP occupies 22.4 L. 1.12 L of gaseous substance = 0.5 g

The molar mass of the substance therefore is 10 g/mol. Example : Determine the mass in grams of 3.50 moles of Copper. Solution: We know that moles are associated with mass in grams, by the relationship Moles of a compound/element = Thus, Moles of copper = 3.50 moles. Molar mass of Cu = 63.55 grams/mol. So, this can be written as: 63.55 g Cu / 1 mole of Cu Multiplying the number of moles with this factor = 3.50 moles of Cu x 63.55 g Cu/1 mole of Cu = 222 grams of Copper Example : Determine the number of moles represented by 237 grams of Strontium. Solution: Molar mass of Strontium = 38 grams/mol. So, Molar mass of Strontium = 38 grams of Sr/ 1 mole of Sr. Multiplying the number of grams by this factor: 237 g of Sr x 1 mole of Sr/38 grams of Sr Moles of Strontium = 6.24 moles. Example : Find the mass in grams of 8.6 moles of Bromine atoms. Solution: Molar mass of Bromine = 80 grams/mol. So, Molar mass of Bromine = 80 grams of Br / 1 mole of Br. Multiplying the number of moles by this factor, = 8.6 moles of Br x 80 grams of Br/1 mole of Br = 688 grams of Br.

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One of the most amazing things about gases is that, despite wide differences in chemical properties, all the gases more or less obey the gas laws. The gas laws deal with how gases behave with respect to pressure, volume, temperature, and amount.

Pressure

Gases are the only state of matter that can be compressed very tightly or expanded to fill a very large space. Pressure is force per unit area, calculated by dividing the force by the area on which the force acts. The earth's gravity acts on air molecules to create a force, that of the air pushing on the earth. This is called atmospheric pressure. The units of pressure that are used are pascal (Pa), standard atmosphere (atm), and torr. 1 atm is the average pressure at sea level. It is normally used as a standard unit of pressure. The SI unit though, is the pascal. 101,325 pascals equals 1 atm. For laboratory work the atmosphere is very large. A more convient unit is the torr. 760 torr equals 1 atm. A torr is the same unit as the mmHg (millimeter of mercury). It is the pressure that is needed to raise a tube of mercury 1 millimeter.

When seventeenth-century scientists began studying the physical properties of gases, they noticed some simple relationships between some of the measurable properties of the gas. Take pressure ( P ) and volume ( V ), for example. Scientists noted that for a given amount of a gas (usually expressed in units of moles [ n ]), if the temperature ( T ) of the gas was kept constant, pressure and volume were related: As one increases, the other decreases. As one decreases, the other increases. We say that pressure and volume are inversely related . There is more to it, however: pressure and volume of a given amount of gas at constant temperature are numerically related. If you take the pressure value and multiply it by the volume value, the product is a constant for a given amount of gas at a constant temperature: P V = constant at constant n and T If either volume or pressure changes while amount and temperature stay the same, then the other property must change so that the product of the two properties still equals

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that same constant. That is, if the original conditions are labeled P 1 and V 1 and the new conditions are labeled P 2 and V 2 , we have P 1 V 1 = constant = P 2 V 2 where the properties are assumed to be multiplied together. Leaving out the middle part, we have simply P 1 V 1 = P 2 V 2 at constant n and T This equation is an example of a gas law. A gas law is a simple mathematical formula that allows you to model, or predict, the behavior of a gas. This particular gas law is called Boyle ' s law , after the English scientist Robert Boyle, who first announced it in 1662. Figure shows two representations of how Boyle ' s law works.

A piston having a certain pressure and volume (left piston) will have half the volume when its pressure is twice as much (right piston). One can also plot P versus V for a given amount of gas at a certain temperature; such a plot will look like the graph on the right. Boyle ' s law is an example of a second type of mathematical problem we see in chemistry-one based on a mathematical formula. Tactics for working with mathematical formulas are different from tactics for working with conversion factors. First, most of the questions you will have to answer using formulas are word-type questions, so the EDUDIGM 1B Panditya Road, Kolkata 29

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first step is to identify what quantities are known and assign them to variables. Second, in most formulas, some mathematical rearrangements (i.e., algebra) must be performed to solve for an unknown variable. The rule is that to find the value of the unknown variable, you must mathematically isolate the unknown variable by itself and in the numerator of one side of the equation. Finally, units must be consistent. For example, in Boyle ' s law there are two pressure variables; they must have the same unit. There are also two volume variables; they also must have the same unit. In most cases, it won ' t matter what the unit is, but the unit must be the same on both sides of the equation. Example : Rita has two cylinders. One is empty and the other contains compressed nitrogen at 25 atm. She wants to distribute the gas in the two cylinders. To do so, she connects the two cylinders. If the volume of the cylinder containing the gas is 50 L and that of the empty one is 80 L, then what will be the pressure inside the two cylinders? Solution: According to Boyles law,

Given, p1 = 25 atm

V1 = 50 L V2 = ( 50 + 80) L = 130 L

Now, 25 atm 50 L = p2 130 L

Hence, the pressure inside the cylinders is 9.62 atm. Example : A sample of gas has an initial pressure of 2.44 atm and an initial volume of 4.01 L. Its pressure changes to 1.93atm. What is the new volume if temperature and amount are kept constant? Solution: First, determine what quantities we are given. We are given an initial pressure and an initial volume, so let these values be P 1 and V 1: P 1 = 2.44 atm and V 1 = 4.01 L We are given another quantity, final pressure of 1.93 atm, but not a final volume. This final volume is the variable we will solve for.

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The Gas Laws P 2 = 1.93 atm and V 2 = ? L Substituting these values into Boyle ' s law, we get (2.44 atm)(4.01 L) = (1.93 atm) V 2

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To solve for the unknown variable, we isolate it by dividing both sides of the equation by 1.93 atm-both the number and the unit: Note that, on the left side of the equation, the unit atm is in the numerator and the denominator of the fraction. They cancel algebraically, just as a number would. On the right side, the unit atm and the number 1.93 are in the numerator and the denominator, so the entire quantity cancels: What we have left is Now we simply multiply and divide the numbers together and combine the answer with the L unit, which is a unit of volume. Doing so, we get V 2 = 5.07 L Does this answer make sense? We know that pressure and volume are inversely related; as one decreases, the other increases. Pressure is decreasing (from 2.44 atm to 1.93 atm), so volume should be increasing to compensate, and it is (from 4.01 L to 5.07 L). So the answer makes sense based on Boyle ' s law. As mentioned, you can use any units for pressure or volume, but both pressures must be expressed in the same units, and both volumes must be expressed in the same units. Example : A sample of gas has an initial pressure of 722 torr and an initial volume of 88.8 mL. Its volume changes to 0.663L. What is the new pressure? Solution: We can still use Boyle ' s law to answer this, but now the two volume quantities have different units. It does not matter which unit we change, as long as we perform the conversion correctly. Let us change the 0.663 L to milliliters: Now that both volume quantities have the same units, we can substitute into Boyle ' s law: The mL units cancel, and we multiply and divide the numbers to get P 2 = 96.7 torr The volume is increasing, and the pressure is decreasing, which is as expected for Boyle ' s law.

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Charless Law

There are other measurable characteristics of a gas. One of them is temperature ( T ). Perhaps one can vary the temperature of a gas sample and note what effect it has on the other properties of the gas. Early scientists did just this, discovering that if the amount of a gas and its pressure are kept constant, then changing the temperature changes the volume ( V ). As temperature increases, volume increases; as temperature decreases, volume decreases. We say that these two characteristics are directly related . A mathematical relationship between V and T should be possible except for one thought: what temperature scale should we use? We know from We can modify this equation as we modified Boyle ' s law: the initial conditions V 1 and T 1 have a certain value, and the value must be the same when the conditions of the gas are changed to some new conditions V 2 and T 2 , as long as pressure and the amount of the gas remain constant. Thus, we have another gas law: This gas law is commonly referred to as Charles ' s law , after the French scientist Jacques Charles, who performed experiments on gases in the 1780s. The tactics for using this mathematical formula are similar to those for Boyle ' s law. To determine an unknown quantity, use algebra to isolate the unknown variable by itself and in the numerator; the units of similar variables must be the same. But we add one more tactic: all temperatures must be expressed in the absolute temperature scale (Kelvin). As a reminder, we review the conversion between the absolute temperature scale and the Celsius temperature scale: K = C +273 where K represents the temperature in kelvins, and C represents the temperature in degrees Celsius. Figure shows two representations of how Charles ' s law works.

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A piston having a certain volume and temperature (left piston) will have twice the volume when its temperature is twice as much (right piston). One can also plot V versus T for a given amount of gas at a certain pressure; such a plot will look like the graph on the right. Example : A sample of gas has an initial volume of 34.8 mL and an initial temperature of 315 K. What is the new volume if the temperature is increased to 559 K? Assume constant pressure and amount for the gas. Solution: First, we assign the given values to their variables. The initial volume is V 1 , so V 1 = 34.8 mL, and the initial temperature is T 1 , so T 1 = 315 K. The temperature is increased to 559 K, so the final temperature T 2 = 559 K. We note that the temperatures are already given in kelvins, so we do not need to convert the temperatures. Substituting into the expression for Charles ' s law yields We solve for V 2 by algebraically isolating the V 2 variable on one side of the equation. We do this by multiplying both sides of the equation by 559 K (number and unit). When we do this, the temperature unit cancels on the left side, while the entire 559 K cancels on the right side: The expression simplifies to

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By multiplying and dividing the numbers, we see that the only remaining unit is mL, so our final answer is V 2 = 61.8 mL Does this answer make sense? We know that as temperature increases, volume increases. Here, the temperature is increasing from 315 K to 559 K, so the volume should also increase, which it does. It is more mathematically complicated if a final temperature must be calculated because the T variable is in the denominator of Charles ' s law. There are several mathematical ways to work this, but perhaps the simplest way is to take the reciprocal of Charles ' s law. That is, rather than write it as Write the equation as It is still an equality and a correct form of Charles ' s law, but now the temperature variable is in the numerator, and the algebra required to predict a final temperature is simpler. Example : A sample of a gas has an initial volume of 34.8 L and an initial temperature of -67C. What must be the temperature of the gas for its volume to be 25.0 L? Solution: Here, we are looking for a final temperature, so we will use the reciprocal form of Charles ' s law. However, the initial temperature is given in degrees Celsius, not kelvins. We must convert the initial temperature to kelvins: -67C +273 = 206 K In using the gas law, we must use T 1 = 206 K as the temperature. Substituting into the reciprocal form of Charles ' s law, we get Bringing the 25.0 L quantity over to the other side of the equation, we get The L units cancel, so our final answer is T 2 = 148 K This is also equal to -125C. As temperature decreases, volume decreases, which it does in this example. Example : It is desired to increase the volume of 5 L of a gas by 40% without changing the pressure. To what temperature should the gas be heated, if its initial temperature is 298 K?

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The Gas Laws Solution: Desired increase in the volume of gas = 40% of 5 L

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Now, V1 = 5 L

T1 = 298 K V2 = 7 L

Therefore,

You may notice in Boyle ' s law and Charles ' s law that we actually refer to four physical properties of a gas: pressure ( P ), volume ( V ), temperature ( T ), and amount (in moles; n ). We do this because these are the only four independent physical properties of a gas. There are other physical properties, but they are all related to one (or more) of these four properties. Boyle ' s law is written in terms of two of these properties, with the other two being held constant. Charles ' s law is written in terms of two different properties, with the other two being held constant. It may not be surprising to learn that there are other gas laws that relate other pairs of properties-as long as the other two are held constant. Here we will mention a few.

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Gay-Lussacs Law

Gay-Lussac ' s law relates pressure with absolute temperature. In terms of two sets of data, Gay-Lussac ' s law is Note that it has a structure very similar to that of Charles ' s law, only with different variables-pressure instead of volume. Example : An iron tank contains helium at a pressure of 3.0 atm at 300 K. The tank

can withstand a maximum pressure of 12.0 atm. The building in which the tank has been placed catches fire. Predict whether the tank will blow up first or melt. (Given, melting point of iron is 1808 K) Solution: To calculate the pressure built up in the tank at the melting point of iron, we have to apply Gay-Lussacs law. According to Gay-Lusaacs Law,

Now,

= 18.08 atm It is found that pressure of the gas in the tank is much more than 12 atm at the melting point. Hence, the tank will blow up before reaching the melting point.

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Avogadros Law

Avogadro ' s law introduces the last variable for amount. The original statement of Avogadro ' s law states that equal volumes of different gases at the same temperature and pressure contain the same number of particles of gas. Because the number of particles is related to the number of moles (1 mol = 6.022 10 23 particles), Avogadro ' s law essentially states that equal volumes of different gases at the same temperature and pressure contain the same amount (moles, particles) of gas. Put mathematically into a gas law, Avogadro ' s law is (First announced in 1811, it was Avogadro ' s proposal that volume is related to the number of particles that eventually led to naming the number of things in a mole as Avogadro ' s number.) Avogadro ' s law is useful because for the first time we are seeing amount, in terms of the number of moles, as a variable in a gas law. Example : A 2.45 L volume of gas contains 4.5 10 21 gas particles. How many gas particles are there in 3.87 L if the gas is at constant pressure and temperature? Solution: We can set up Avogadro ' s law as follows: We algebraically rearrange to solve for n 2 : The L units cancel, so we solve for n 2 : n 2 = 7.1 10 21 particles The variable n in Avogadro ' s law can also stand for the number of moles of gas in addition to number of particles. One thing we notice about all the gas laws is that, collectively, volume and pressure are always in the numerator, and temperature is always in the denominator. This suggests that we can propose a gas law that combines pressure, volume, and temperature. This gas law is known as the combined gas law , and its mathematical form is This allows us to follow changes in all three major properties of a gas. Again, the usual warnings apply about how to solve for an unknown algebraically (isolate it on one side of the equation in the numerator), units (they must be the same for the two similar variables of each type), and units of temperature must be in kelvins. Example : A sample of gas at an initial volume of 8.33 L, an initial pressure of 1.82 atm, and an initial temperature of 286 K simultaneously changes its temperature to 355 K and its volume to 5.72 L. What is the final pressure of the gas? Solution: We can use the combined gas law directly; all the units are consistent with each other, and the temperatures are given in Kelvin. Substituting, EDUDIGM 1B Panditya Road, Kolkata 29

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We rearrange this to isolate the P 2 variable all by itself. When we do so, certain units cancel: Multiplying and dividing all the numbers, we get P 2 = 3.29 atm Ultimately, the pressure increased, which would have been difficult to predict because two properties of the gas were changing. As with other gas laws, if you need to determine the value of a variable in the denominator of the combined gas law, you can either cross-multiply all the terms or just take the reciprocal of the combined gas law. Remember, the variable you are solving for must be in the numerator and all by itself on one side of the equation.

It is clear from Boyles law and Charles law that the volume of a given mass of gas depends upon the temperature and pressure of the gas. Thus, for comparing the masses or densities of two or more gases having same volume, we need to standardise the temperature and pressure at which the volume of the gases is measured. The standard temperature and standard pressure for all gases is known as the standard temperature and pressure. In short form, it is written as S.T.P. The standard pressure-temperature is taken as 0C or 273 K. The standard pressure is taken as 1 atm or 760 mm of mercury. One mole of gas occupies a volume of 22.4 litres at STP (standard temperature and pressure conditions i.e. 273 K and 1 atm). Here is an application of this: A gas X occupies a volume of 512 cm3. at S.T.P. What will be the volume occupied by X at 300 K and at a pressure of 720 mm? According to the gas equation,

Here, initial pressure of the gas, p1 = standard pressure = 760 mm of mercury EDUDIGM 1B Panditya Road, Kolkata 29

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The Gas Laws Final pressure of the gas, Pp2 = 720 mm Initial volume of the gas, V1 = 512 cm3 Final volume of the gas, V2 = ? Initial temperature of the gas, T1 = standard temperature = 273 K Final temperature of the gas, T2 = 300 K

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Now,

Hence, the volume of the gas occupied by X at 300 K and at a pressure of 720 mm will be 593.89 cm3.

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So far, the gas laws we have considered have all required that the gas change its conditions; then we predict a resulting change in one of its properties. Are there any gas laws that relate the physical properties of a gas at any given time? Consider a further extension of the combined gas law to include n . By analogy to Avogadro ' s law, n is positioned in the denominator of the fraction, opposite the volume. So Because pressure, volume, temperature, and amount are the only four independent physical properties of a gas, the constant in the above equation is truly a constant; indeed, because we do not need to specify the identity of a gas to apply the gas laws, this constant is the same for all gases. We define this constant with the symbol R , so the previous equation is written as which is usually rearranged as PV = nRT This equation is called the ideal gas law . It relates the four independent properties of a gas at any time. The constant R is called the ideal gas law constant. Its value depends on the units used to express pressure and volume. Table: Values of the Ideal Gas Law Constant R Numerical Value Units 0.08205 62.36 8.314 The ideal gas law is used like any other gas law, with attention paid to the unit and making sure that temperature is expressed in Kelvin. However, the ideal gas law does not require a change in the conditions of a gas sample . The ideal gas law implies that if you know any three of the physical properties of a gas, you can calculate the fourth property. Example : A 4.22 mol sample of Ar has a pressure of 1.21 atm and a temperature of 34C. What is its volume? Solution: The first step is to convert temperature to kelvins: 34 +273 = 307 K EDUDIGM 1B Panditya Road, Kolkata 29

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The Gas Laws Now we can substitute the conditions into the ideal gas law:

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The atm unit is in the numerator of both sides, so it cancels. On the right side of the equation, the mol and K units appear in the numerator and the denominator, so they cancel as well. The only unit remaining is L , which is the unit of volume that we are looking for. We isolate the volume variable by dividing both sides of the equation by 1.21: Then solving for volume, we get V = 87.9 L Example : At a given temperature, 0.00332 g of Hg in the gas phase has a pressure of 0.00120 mmHg and a volume of 435 L. What is its temperature? Solution: We are not given the number of moles of Hg directly, but we are given a mass. We can use the molar mass of Hg to convert to the number of moles. Pressure is given in units of millimeters of mercury. We can either convert this to atmospheres or use the value of the ideal gas constant that includes the mmHg unit. We will take the second option. Substituting into the ideal gas law, The mmHg, L, and mol units cancel, leaving the K unit, the unit of temperature. Isolating T all by itself on one side, we get Then solving for K, we get T = 1,404 K The ideal gas law can also be used in stoichiometry problems. Example : What volume of H 2 is produced at 299 K and 1.07 atm when 55.8 g of Zn metal react with excess HCl? Zn(s) +2HCl(aq) -ZnCl 2 (aq) +H 2 (g) Solution: Here we have a stoichiometry problem where we need to find the number of moles of H 2 produced. Then we can use the ideal gas law, with the given temperature and pressure, to determine the volume of gas produced. First, the number of moles of H 2 is calculated: Now that we know the number of moles of gas, we can use the ideal gas law to determine the volume, given the other conditions: All the units cancel except for L, for volume, which means

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It should be obvious by now that some physical properties of gases depend strongly on the conditions. What we need is a set of standard conditions so that properties of gases can be properly compared to each other. Standard temperature and pressure (STP) is defined as exactly 100 kPa of pressure (0.986 atm) and 273 K (0C). For simplicity, we will use 1 atm as standard pressure. Defining STP allows us to compare more directly the properties of gases that differ from each other. One property shared among gases is a molar volume. The molar volume is the volume of 1 mol of a gas. At STP, the molar volume of a gas can be easily determined by using the ideal gas law: All the units cancel except for L, the unit of volume. So V = 22.4 L Note that we have not specified the identity of the gas; we have specified only that the pressure is 1 atm and the temperature is 273 K. This makes for a very useful approximation: any gas at STP has a volume of 22.4 L per mole of gas ; that is, the molar volume at STP is 22.4 L/mol ( Figure6.4, " Molar Volume " ). This molar volume makes a useful conversion factor in stoichiometry problems if the conditions are at STP. If the conditions are not at STP, a molar volume of 22.4 L/mol is not applicable. However, if the conditions are not at STP, the combined gas law can be used to calculate what the volume of the gas would be if at STP; then the 22.4 L/mol molar volume can be used. A mole of gas at STP occupies 22.4 L, the volume of a cube that is 28.2 cm on a side.

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The ideal gas law can also be used to determine the densities of gases. Density, recall, is defined as the mass of a substance divided by its volume: Assume that you have exactly 1 mol of a gas. If you know the identity of the gas, you can determine the molar mass of the substance. Using the ideal gas law, you can also determine the volume of that mole of gas, using whatever the temperature and pressure conditions are. Then you can calculate the density of the gas by using Example : What is the density of N 2 at 25C and 0.955 atm? Solution: First, we must convert the temperature into kelvins: 25 +273 = 298 K If we assume exactly 1 mol of N 2 , then we know its mass: 28.0 g. Using the ideal gas law, we can calculate the volume: All the units cancel except for L, the unit of volume. So V = 25.6 L Knowing the molar mass and the molar volume, we can determine the density of N 2 under these conditions: Example : A vessel of 200 mL capacity contains a certain amount of gas at 27C and 0.9 bar pressure. The gas is then transferred into another vessel of capacity 150 mL at 27C. What would be the pressure of the gas in the vessel of capacity 150 mL? Solution: According to combined gas law,

Here, initial pressure of the gas, p1 = 0.9 bar Final pressure of the gas, p2 = ? Initial volume of the gas, V1 = 200 mL Final volume of the gas, V2 = 150 mL Initial temperature of the gas, T1 = (27 + 273) K = 300 K Final temperature of the gas, T2 = (27 + 273) K = 300 K

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Now,

= 1.2 bar Hence, the pressure of the gas in the vessel of capacity 150 mL would be 1.2 bar. Example : How many grams of nitrogen are present in an 8.21 L sample of a gas at 5 atm and 23C? Solution: It is given that,

Here, R = 0.0821 L atm K1 mol1 From the ideal gas equation, we have

pV = nRT

= = 2 mol Molecular mass of nitrogen = 28 g This means that 1 mole of nitrogen molecules contains 28 g of nitrogen. Therefore, 2 moles of nitrogen molecules contain 2 28 g, i.e., 56 g of nitrogen.

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Thus, at 5 atm and 23C, 56 g of nitrogen gas are present in an 8.21 L sample of the gas.

Gases were among the first substances studied in terms of the modern scientific method, which was developed in the 1600s. It did not take long to recognize that gases all shared certain physical behaviors, suggesting that all gases could be described by one all-encompassing theory. Today, that theory is thekinetic theory of gases . It is based on the following statements: 1. Gases consist of tiny particles of matter that are in constant motion. 2. Gas particles are constantly colliding with each other and the walls of a container. These collisions are elastic; that is, there is no net loss of energy from the collisions. 3. Gas particles are separated by large distances, with the size of a gas particle tiny compared to the distances that separate them. 4. There are no interactive forces (i.e., attraction or repulsion) between the particles of a gas. 5. The average speed of gas particles is dependent on the temperature of the gas.

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The kinetic theory of gases describes this state of matter as composed of tiny particles in constant motion with a lot of distance between the particles. This model of gases explains some of the physical properties of gases. Because most of a gas is empty space, a gas has a low density and can expand or contract under the appropriate influence. The fact that gas particles are in constant motion means that two or more gases will always mix, as the particles from the individual gases move and collide with each other. An ideal gas is a gas that exactly follows the statements of the kinetic theory. Unfortunately, real gases are not ideal. Many gases deviate slightly from agreeing perfectly with the kinetic theory of gases. However, most gases adhere to the statements so well that the kinetic theory of gases is well accepted by the scientific community.

Breathing (more properly called respiration ) is the process by which we draw air into our lungs so that our bodies can take up oxygen from the air. Let us apply the gas laws to breathing. Start by considering pressure. We draw air into our lungs because the diaphragm, a muscle underneath the lungs, moves down to reduce pressure in the lungs, causing external air to rush in to fill the lower-pressure volume. We expel air by the diaphragm pushing against the lungs, increasing pressure inside the lungs and forcing the highpressure air out. What are the pressure changes involved? A quarter of an atmosphere? A tenth of an atmosphere? Actually, under normal conditions, it ' s only 1 or 2 torr of pressure difference that makes us breathe in and out. Breathing involves pressure differences between the inside of the lungs and the air outside. The pressure differences are only a few torr. A normal breath is about 0.50 L. If room temperature is about 22C, then the air has a temperature of about 295 K. With normal pressure being 1.0 atm, how many moles of air do we take in for every breath? The ideal gas law gives us an answer: Solving for the number of moles, we get n = 0.021 mol air This ends up being about 0.6 g of air per breath-not much but enough to keep us alive.

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Key Takeaways

Pressure is a force exerted over an area. Pressure has several common units that can be converted.

The behavior of gases can be modeled with gas laws. Boyle ' s law relates a gas ' s pressure and volume at constant temperature and amount. Charles ' s law relates a gas ' s volume and temperature at constant pressure and amount. In gas laws, temperatures must always be expressed in kelvins. There are other gas laws that relate any two physical properties of a gas. The combined gas law relates pressure, volume, and temperature of a gas.

The physical behavior of gases is explained by the kinetic theory of gases. An ideal gas adheres exactly to the kinetic theory of gases.

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