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Preliminary Chemistry Topic 3

What is this topic about?

WATER

To keep it as simple as possible, (K.I.S.S.) this topic involves the study of: 1. THE IMPORTANCE OF WATER 2. STRUCTURE, BONDING & PROPERTIES OF WATER 3. THE CHEMISTRY OF AQUEOUS SOLUTIONS 4. HEAT CAPACITY & CALORIMETRY ...all in the context of waters vital role in the natural world

but first, an introduction...


Water... Amazing Stuff !
Its seems very strange to devote an entire topic to just one simple compound. But water is so important in so many ways...

Chemically...
You already know several different ways to describe and visualize the water molecule...

H2O
H O H

O H

all life on Earth depends on WATER

In this topic you will learn more about the within and between water molecules, and how this is responsible for waters many unique properties. You will learn about the and how we measure concentrations, and calculate with
Photos by Diana

Chemical Bonding
Chemistry of Solubility

WATER is involved in our life & leisure

WATER...
covers most of the Earth controls weather and climate carves landscapes makes up 75% of all living things dissolves things absorbs heat
Preliminary Chemistry Topic 3 Copyright 2005-2007 keep it simple science

Molarity of solutions.
Finally, as a lead-in to Topic 4, you will learn about waters quite remarkable Heat Capacity, and how we use it in the technique of

Calorimetry for measuring energy changes


during chemical processes. 1 www.keepitsimplescience.com.au

...and much more

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CONCEPT DIAGRAM (Mind Map) OF TOPIC


Some students find that memorizing the OUTLINE of a topic helps them learn and remember the concepts and important facts. As you proceed through the topic, come back to this page regularly to see how each bit fits the whole. At the end of the notes you will find a blank version of this Mind Map to practise on. Comparison of Properties

The Many Roles of Water on Earth

Basic Properties: Density, m.p. & b.p.

Water Content of the Earths Spheres

Bonding in Water and Similar Molecules CH4 NH3 H2S

Polar Covalent Bonding

Importance of Water

Structure, Bonding & Properties of Water

Dipoles & Hydrogen Bonds

More Unusual Properties of Water; Surface Tension & Viscosity

WATER
Heat Capacity & Calorimetry

Water as a Solvent

Chemistry of Aqueous Solutions

How Ionic & Polar Substances Dissolve

Waters Heat Capacity & Life on Earth. Thermal Pollution

Temperature, Heat Energy & Specific Heat Capacity

Ionic Solutions & Equations

Calorimetry & Calorimeters

Heat of Solution

Measuring Concentration; Molarity

Dynamic Equilibrium in a Saturated Solution

Endothermic & Exothermic Changes

Precipitation Reactions

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1. THE IMPORTANCE OF WATER


Water in the Spheres of the Earth
In the Atmosphere, water is present as water vapour, and as tiny liquid droplets in the clouds.

Revision:

Solutions, Solute and Solvent

A SOLUTION is a mixture, usually of a solid (the SOLUTE) and a liquid (the SOLVENT). The solute and solvent particles are intimately associated so that the mixture cannot be separated by filtration, and the solute will never settle to the bottom. We say the solute is dissolved in the solvent.

The Many Roles of Water on Earth


Water is essential in all living things because it is a solvent for all the chemicals in a living cell, and the medium in which all the chemical reactions occur. a reactant or product in many biological reactions, such as photosynthesis and cellular respiration. a transport medium for carrying substances, such as when food, oxygen, etc. are carried in the blood. a shock-absorber and support structure. Many plants and simple animals (e.g. worms) rely on water pressure in their tissues to hold their body in shape. Our brain and other body parts are cushioned by water-based body fluids. a habitat (place to live) for many species. Water habitats have very stable temperatures because of waters ability to absorb heat with little temperature change.

In percentage terms, water makes up between 1% and 5% of the air, varying with time, place and weather. In the Lithosphere, water makes up about 10% of the solid Earth. Although solid rock and minerals seem perfectly dry, there is often water incorporated into the crystal lattice structure of many minerals. When volcanoes erupt, a huge amount of steam is released as the rocks are melted. The Hydrosphere is, of course, nearly all water. Oceans contain about 3% dissolved salt, but the ice caps, rivers and lakes are virtually 100% water. In Living Things, water makes up about 75% of every lifeform, but jellyfish or watermelons are more like 95%

Photo by Krys Squires

Water in the landscape


snow

clouds eroded valley

Water is a major factor in global climate, weather and the shaping of landforms. The water-cycle produces all rain, hail and snowfall. Water is the main agent of erosion, carving out the valleys and wearing down the mountains, creating the landscapes. Water can absorb, transport and release vast amounts of heat energy. The ocean currents largely control global climates by re-distributing heat world-wide. For humans and their civilization, water is a major resource for drinking, cooking, washing and recreation. for crop irrigation and farming. in industry as a solvent, cleaning agent and cooling agent. for transport by boat and ship. for generating hydro-electricity. 3 www.keepitsimplescience.com.au

Glacier

ll fa r te Wa

Photo by Diana

Lake

Belinda

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Basic Properties of Water


You may have done some simple practical work to investigate some of the basic properties of water.

Waters Density Anomaly


For almost every pure substances the solid is more dense than the liquid. Water is the opposite... liquid water has a higher density than ice. How do we explain this? In solid water (ice) the molecules form a molecular lattice. Each molecule is held rigidly in place.

Density of Liquid & Solid Water


Density is the ratio between the mass of a substance and the space (volume) it occupies. All pure substances have a fixed and characteristic density. Density = Mass Volume D= m V A simple method is to weigh an empty, dry measuring cylinder, then fill with water. Read the volume of water accurately then reweigh to get the mass of water. Ideally, you would repeat these measurements with different volumes of water. For ice, you need to weigh it quickly before it melts. If the ice cubes really are cubes or rectangular prisms, you might measure length, width and height, then calculate the volume. Typical Results Liquid water: Mass = 245 g Volume = 250mL

When ice melts to form liquid water, the molecules have enough energy to move around freely. However, they are still very close together, and in fact they wriggle in even closer to each other than when rigidly arranged in the solid lattice. Now there is the same mass of particles crammed into less space... higher density.

Since solid ice has a lower density, it floats in liquid water.

D = m = 245 = 0.98 g/mL V 250 Ice: Mass = 33 g Volume = 36mL

Melting & Boilingo Points

Pure water melts at 0 C, and boils at 100oC, under normal 1 atmosphere of pressure. (As you may know, the celsius temperature scale is based on the m.p. & b.p. of water.) Under different pressures, or if impure, the m.p. and b.p. will change. For example, it can be difficult to get a good, hot cup of tea on a high mountain, because at the lower air pressure the water boils at a much lower temperature. You may have done experiments to find out the effect of impurities on the boiling point. A common experiment is to boil water with, and without, an additive such as salt and measure the boiling temperature. It will usually be found that the boiling temperature rises by several degrees with solute dissolved in it. 4 www.keepitsimplescience.com.au

D = m = 33 = 0.92 g/cm3 V 36 Note: When measuring volume, we normally measure liquids in millilitres (mL) and solids in cubic centimetres (cm3). For practical purposes these are equal volumes.

Density changes with temperature. Water achieves its highest density at 4oC. This value is 1.00 g/mL
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2. STRUCTURE, BONDING & PROPERTIES OF WATER


Water the Weirdo!
We are so familiar with the everyday properties of water that we do not realize how unusual and strange water is, until we make a careful comparison with other, similar compounds. Some of these properties will be studied in this topic, but heres a preview: The Strange Properties of Water Abnormally high m.p. and b.p. Abnormally high viscosity and surface tension Abnormally high Heat Capacity Unusual Density anomaly (already described) ... when compared to similar sized molecules. Why? Its all a matter of bonding... The result is that the ammonia molecule is a triangular pyramid shape. Water H2O Lewis Formula
H O H

Ammonia NH3 Lewis Formula


H N H H

Structural formula

N H

In this molecule, the 4 pairs of electrons surrounding the nitrogen atom are also at the points of a tetrahedron.

However, one pair is not involved in a covalent bond... it is an unbonded pair, but still occupies a point of the tetrahedron.

Bonding in Molecular Compounds of Hydrogen


To understand water, we need to compare it to other, similar sized, covalent molecules containing hydrogen: Methane CH4 Structural formula

H C H H

Structural formula

O H

Lewis Formula
H H C H H Covalent bonds (shared pairs of electrons)

In the water molecule there are two unbonded pairs occupying 2 of the points of the tetrahedron.

The Lewis Formula, and the structural formula, would suggest that the molecule is a flat, box-shape. However, the pairs of electrons in each covalent bond always try to get as far away from each other as possible, and in 3-dimensions this results in a tetrahedron shape (a regular, triangular pyramid with 4 points as far apart as possible).

Therefore, the water molecule is bent. o The diagrams suggest a 90 right angle between the hydrogen atoms, but in 3-D it is more like 105o. Hydrogen sulfide H2S has exactly the same bonding geometry as water. The central sulfur atom is larger than oxygen, but otherwise the molecules are very similar. Lewis formula
H S H

Structural formula

S H

Each point of a tetrahedron is as far away from the other 3 as it can get. In the methane molecule, each covalent bond (and therefore each hydrogen atom) is as far away from the other 3 as it can get.
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Comparing the Properties of These Compounds


The 4 compounds CH4, NH3, H2O and H2S are of comparable size and bonding. Now we compare their melting and boiling points, and how these are related to their relative molecular weights. Compound CH4 NH3 H2O H2S Molecular Weight 16 17 18 34 m.p. (oC) -183 -78 0 -86 b.p. (oC) -162 -33 100 -60

Polar Covalent Bonding


To understand water better, you must learn more about covalent and ionic chemical bonding. Up to this point, you have seen these types of bonding as quite different things. Now you must realize that they are really different degrees of the same thing. An analogy might help... Imagine sharing some lollies with another person. If both of you are very fair about it, and neither dominates or intimidates the other, the sharing will be equal:
My Share Your Share

This is like a pure covalent bond where electrons are shared evenly An ionic bond can be thought of as the lolly-sharing between a hungry bully and a wimp who hates lollies anyway:
Bully s s Share Gimme everything available Wimp s s Share I didnt want those anyway When electrons are shared so unequally, the result is (+ve) and (-ve) ions being formed.

H2O

Graph of m.p. & b.p. for these compounds


ng ili bo

Melting Points & Boiling Points (oC) -1 100 0

100

NH3

me ltin gp oin ts

ts in po

H2S

-2 200

CH4
15 20

e lin nd e r dt cte pe x E

Now you must learn that there is also a situation (or a whole heap of situations) in between these extremes, where the lollies will be shared, but perhaps not evenly. Sharing, but not evenly. In chemical bonding, this kind of sharing is called a Polar Covalent Bond and occurs when electrons are shared between 2 atoms with quite different values for Electronegativity. (This was introduced in Topic 2... revise)
A Pure Covalent Bond occurs when electrons are shared evenly. In a Polar Covalent Bond the sharing is not even. The electrons are attracted more to one atom than the other.
dipole This is a d It has 2 opposite poles

25 30 35 Molecular Weight

Usually, the m.p.s & b.p.s of comparable substances show a steady increase as the atomic or molecular weight increases. This graph shows that both water and ammonia have unusually high melting and boiling points. Water especially has values way above those of comparable molecules. Why? Whats going on?

In Topic 1 you learned how the properties of m.p. & b.p. are controlled by the bonding within substances. Covalent molecules are held together internally by strong covalent bonds (intra-molecular bonds). These however, are not the bonds that must be overcome to melt or boil the substance. Its the forces between the molecules (inter-molecular bonds) that must be overcome to melt or boil a molecular substance. In water, it seems these forces are unusually strong!
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This causes the bond (and perhaps the entire molecule) to become electrically polarized. The electric charge is not evenly distributed. One end has a greater concentration of electrons and has a slight negative charge (), while the other end becomes slightly positive (+). The Greek letter delta () is used to denote a small amount of something, in this case electric charge. The molecule is called a dipole, meaning it has 2 poles.

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Polar Bonds Create Inter-Molecular Forces


The charges on each end of a molecular dipole are only a fraction of the size of the charges on an ion, but they do cause electrical forces to occur between nearby molecules.

Hydrogen Bonding in Water


In the water molecule the covalent bonds are very polar, so the atoms develop especially large partial charges. Each molecule is a dipole, and strong inter-molecular Hydrogen Bonds attracts each molecule to its neighbours.

+ +
These forces are called Dipole-Dipole Forces

+ +
+
Inter-molecular Hydrogen Bonds between molecules

+
Intra-molecular Covalent Bonds within molecules

It is these forces which are the inter-molecular forces that hold the molecules together in the solid state. These are the forces which must be overcome with thermal energy in order for the solid to melt. These are the forces which determine the m.p. and b.p. of a molecular substance. The strength of the dipole-dipole force varies according to the degree of polarity of the covalent bond (how evenly or unevenly the electrons are being shared) and also varies according to the shape of the molecule. In some substances the forces are very weak, in others quite strong. The strongest dipole-dipole forces are about 1/3 as strong as a full-scale ionic bond. These occur whenever hydrogen atoms are bonded to Oxygen, Nitrogen or Fluorine, and are called... Hydrogen Bonds Oxygen, Nitrogen and Fluorine are all small, strongly electronegative atoms. Hydrogen is even smaller, and once the electrons are sucked away from it in the polar bond, the hydrogen atom is really a naked proton.
O, N or F atom H atom

It is this network of hydrogen bonds that holds the molecules in a rigid lattice in the solid state. The Hydrogen Bonding is the reason that ice has such a high melting point, compared to other molecules. (Ammonia also has relatively high m.p. & b.p... same reason!) Once melted to a liquid, the molecules can move around, but cling to each other because of the hydrogen bonds. The molecules even wriggle closer to each other and the density increases. To boil water to a gas, the molecules must be able to totally break free from the hydrogen bonds. This requires considerable energy, so water has an unusually high boiling point, compared to other molecules.

Polar Covalent Bond

Hydrogen Bond

The result is an especially strong set of partial charges, a powerful dipole, and strong inter-molecular force, which attracts nearby molecules to each other. These especially strong dipole-dipole attractions are called

Hydrogen Bonds.

It is the HYDROGEN BONDING between water molecules which explains all of waters weird and unusual properties 7

Photo by Mario Magallanes Trejo

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More of Waters Unusual Properties


As well as the Density Anomaly and the very high m.p. and b.p., water has other properties which, compared to other similar size molecules, are quite extraordinary. You may have done simple practical work to demonstrate these: Surface Tension is a phenomenon where a liquid acts as if it has a skin at the surface. In most liquids the effect is small, but water has a relatively strong surface tension.

Viscosity is another phenomenon you may have experimented with. Viscosity is a measure of how sticky or thick a liquid is. Technically it is measured as the resistance of a liquid to flowing through a thin tube, but it can be thought of as how easy or difficult it is for things to move through the liquid.

You may have dropped marbles into various liquids and compared the rates at which they fell, as a way to observe viscosity differences. Liquids like oil are very viscous, so you may get the idea that water has a low viscosity. Yes it has, compared to oil, but thats not really a fair comparison. In fact, when the viscosity of water is compared to liquids with similar size molecules, waters viscosity is very high. Why? Its that hydrogen bonding again... The hydrogen bonds between water molecules cause them to cling to each other, and make it much more difficult for a moving object to move through the liquid.

A piece of metal being supported on the surface tension of water

Technically, the metal is NOT floating. The explanation is, as usual, hydrogen bonding. Water molecules have a network of forces attracting them to each other. At the surface, this network of force resists penetration and can support objects which will sink if pushed through the skin. Surface tension is also the reason that water forms droplets.

The high viscosity of water has had a major impact on the evolution of any aquatic animals who need to move quickly to catch food or escape predators.

Fast moving aquatic animals are always streamlined in shape and equipped with powerful tails or flippers for propulsion.
Photo by Diana Photo by Natasha Whiteley

The surface tension network of forces tries to pull the droplet into a spherical shape. The dew-drops in the photo are hanging on a spider web.

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Worksheet 1
Part A Fill in the blanks In the atmosphere, water is present as a)................................. and as tiny liquid droplets in the b)................................... In the lithosphere, water makes up about c)..............% of solid rock, embedded as part of the d)............................................. structure of many minerals. The e)........................................... is almost 100% water, most of it liquid in the f)...................., but some as solid ice in the polar g)....................................... and glaciers. In living things, water makes up about h)......% of every living cell. Water is essential to all living things because: it is the i).................................... for all the chemicals of life. it is involved in many important j)......................................... it k)................................... substances around the body. it l)............................ and ............................. body organs. it is a m)................................. for plants & animals to live in. Water environments have very n)........................................ temperatures, because of waters ability to o)......................... .................................... without much temperature change. Water is important in controlling p)............................... and weather, and is a major agent of q)................................ For human society, water is a major resource for drinking, r)............................, washing and s).......................... for crop t).................................. in farming.

in industry, as a u).........................., and cleaning and cooling agent. for generating v)........................................................ At normal atmospheric pressure, pure water melts at w).........oC and boils at x)..........oC. Its density is y)...............g/mL, but (very unusually) the density of ice is z).......................... (more/less) than liquid water. This is because in the liquid, the molecules actually get aa)............................ to each other than when rigidly lined up in the molecular ab)............................. of ice. Part B Practice Problems Density 1. Complete the table of values Sample Mass Volume (g) (mL or cm3) A 150 17 B 22 18 C 65 (c) D 210 290 E (e) 85 F 6.8 f) D = m/V Density (a) (b) 13.5 (d) 3.1 1.2

2. a) Which 2 samples in the table might be the same substance? Explain your answer. b) Which substance in the table would float in water? Explain.

Worksheet 2

Fill in the blank spaces. Check answers at the back. Water has a number of unusual a)................................... including abnormally high m.p & b.p. and the density anomaly. These are all due to the b)..................................... between the molecules. When an atom has 4 pairs of electrons around it (as is the case in most covalent molecules) each pair tries to stay c)..................................................................... as possible. The result is that each pair lies at one of the points of a d)................................................. This is why methane is a tetrahedral shaped molecule. In ammonia, the central e)................................ atom is bonded to 3 f)............................. atoms but also has an g)....................................... electron pair occupying one point of the tetrahedron. Therefore, the molecule is a h).......................................... shape. In water, the oxygen atom has 2 pairs of i)..................................................... occupying 2 points of the tetrahedron. This results in the molecule being j)........................ (shape) In a pure covalent bond, the electrons are shared k)................................... An ionic bond occurs when the sharing is totally uneven so that ions form. In between these extremes there are l).............................. covalent bonds in which the sharing is m).................................. The result is that n)............................ electric charges (denoted by the greek letter ) are produced on the molecule because of the uneven distribution of electrons.
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The molecule is said to be a o)......................................... because it has 2 electric poles. The small charges on the o).............................. are not as large as the charge on an ion, but do create forces of p)........................................... between each molecule and its neighbours. These q)....................... - ............................. forces tend to hold molecules together. These are the r)..............molecular forces which must be overcome for a substance to change s)........................... When hydrogen is bonded to atoms of t)..............................., ..................................... or .................................... the forces are especially strong. These are called u)...................................... Bonds. Water is such a molecule. The molecules are strongly attracted to each other by the u)............................. bonds. This means that the m.p. & b.p. are abnormally v).................. compared to similar sized molecules. Another result of the hydrogen bonding is that water has a very strong w)................................................. which acts like a skin and can support small objects which will x)................................... if placed under the surface. Water also has a relatively high y).................................... due to the way the molecules cling to each other. Because of this, many aquatic animals are z)........................................ to allow easier movement through the water. 9 www.keepitsimplescience.com.au

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3. THE CHEMISTRY OF AQUEOUS SOLUTIONS


Water as a Solvent
Perhaps the main reason that water is so important to living things, and in the study of Chemistry is that it is a great solvent. This doesnt mean that everything will dissolve in water... far from it. You may have done experimental work to try to find any general rules about which substances will, or will not, dissolve in water. Generally, it all depends on the type of bonding within the substance. Ionic Compounds are (generally) soluble in water, and all because water molecules are polar. Ionic compounds are composed of a strong ionic crystal lattice. It requires a high temperature to melt this lattice, but water molecules can dissolve the crystal by surrounding each ion and detaching it from the lattice.
Ions h hydrated (surrounded by water molecules) and taken into solution

Covalent Molecular Substances may, or may not dissolve, in water depending on their own polar nature, and on how large the molecules are. If the solute molecules are themselves polar, they will generally dissolve, because the water molecules will surround each molecule, attracted by dipole-dipole forces. In the case of ethanol (CH3CH2OH) (alcohol) the water molecules form hydrogen bonds with the ethanol molecules which contain the highly polar -OH chemical group.
Water molecules form hydrogen bonds and h hydrate the molecule so it dissolves

+ +

Na
+

Ethanol +

CH3CH2OH

Cl-

+ +

There are many covalent molecules like this, with -NH or -OH groups on the molecule, including all the alcohols and the sugars such as sucrose (table sugar). Small, non-polar covalent molecules such as iodine (I2), oxygen (O2) and nitrogen (N2) will dissolve in water, but only in small amounts... we say they are sparingly soluble. These molecules do not have any dipole charges to attract a water molecule and become hydrated, but they are so small and have such small dispersion forces holding them to each other, that they can simply spread out, in small numbers, among the water molecules. Dispersion Forces are extremely weak attractive forces that exist within all substances. Among non-polar molecules they are the only inter-molecular forces acting to hold the molecules together. This is why such substances have very low m.p. & b.p. Knowledge of how and why these forces arise is not required for this course. Larger non-polar molecules will NOT dissolve in water. They are too large to simply disperse among the water molecules, and there are no dipoles for the water molecules to associate with or form hydrogen bonds. These substances include petrol, oils and waxes, and are often described as hydrophobic (= water hating/fearing) because they will not mix with water. 10 www.keepitsimplescience.com.au

Na+
+

Cl-

Na+

Cl

Na+
Lattice disintegrating

ClIonic Lattice

Na+

Cl-

Na+

Cl-

Na+

Cl-

Na+

Notice how the the (+ve) ions are surrounded by water molecules which are presenting the () end of their dipole to the ion. The (-ve) ions are surrounded by molecules presenting the (+) end of the dipole. With each ion surrounded by dozens of water molecules, the attraction between the ions is blanketed and the individual ions can no longer get close enough to each other for their charges to bond them together. An ionic compound in solution is made up of free moving, separate, hydrated ions.

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A Special Case to Know About... Hydrogen Chloride


In the pure state, the compound hydrogen chloride (HCl) is composed of small polar molecules:
+ HCl molecules +

Water as a Solvent (continued)


Covalent Network Substances like the elements Silicon and Carbon, and compounds like silicon dioxide SiO2 (the mineral silica), are crystal lattices of atoms bonded together covalently.

Despite the dipole-dipole attractions, the m.p. & b.p. are quite low, so pure HCl is a gas at room temperature. You would expect that these molecules would dissolve in water, but they do much more than just dissolve... they interact so strongly with water that the molecules ionize and become separate H+ and Cl- ions.
+ HCl(g) molecule

Since the bonds are non-polar, or only slightly polar, water molecules are not attracted, and the substance will NOT dissolve. Compounds with Very Large Molecules Living cells produce many very large molecules, each containing perhaps tens of thousands of atoms. Some, like cellulose (in plant cell walls) contain many polar groups, and water molecules will be attracted and form hydrogen bonds. However, the cellulose molecules are often linked together by their own hydrogen bonding, and covalent cross-linking, and it is impossible for the huge molecules to be taken into solution. Cellulose is therefore insoluble, but is described as being hydrophilic (= water loving) because water will cling to it, wet it and soak into it very well. Some protein molecules will dissolve if they have a folded, globular shape that allows water molecules to surround them. This is the case with enzyme proteins, which are dissolved in the water inside a cell, or in the blood. Other proteins, like keratin (in hair and skin) are in long chains that cross-link to others. They will not dissolve, but are hydrophilic. Plastics, such as polyethylene, are composed of huge molecules too. Most are non-polar, and may be cross-linked with each other. They tend to be insoluble in water and are generally hydrophobic. Like dissolves like... water is polar, so it dissolves: ionic compounds polar molecules (unless too large) very small non-polar molecules (sparingly)

Cl
+

+ +

Cl-(aq) and H+(aq)

Separate, hydrated ions

Hydrogen chloride dissolved in water is, of course, hydrochloric acid. This is more than just dissolving in water because the molecule has ionized... what was a polar covalent bond has become ionic, due the the influence of the polar water molecule.

HCl(g)

H+(aq)

Cl-(aq)

Molecules in the gas state.

(aq) means aqueous. This is Latin for in water. In an equation it means dissolved and hydrated by water molecules.

This equation describes the dissolving of HCl gas to form hydrochloric acid.
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Ionic Solutions

Dynamic Equilibrium in a Saturated Solution


If you keep adding and stirring salt into water until the solution is saturated, you reach a dynamic equilibrium between the ions still in an undissolved, solid, crystal lattice, and those in the solution as separate, hydrated ions. For simplicity in this diagram, the water molecules have been left out.

When an ionic compound dissolves in water, the crystal lattice disintegrates and the (+ve) and (-ve) ions become separately hydrated to form the solution. Dissolving of sodium chloride: NaCl(s) Na+(aq) + Cl (aq)
-

The positive (+ve) ions are collectively called cations. Negative (-ve) ions are known as anions. You need to be able to write an equation to describe the dissolving of any ionic compound. More examples: Dissolving of magnesium nitrate: Mg(NO3)2(s) Mg+2(aq) + 2NO3 (aq)
This ion precipitates Ions in a saturated solution

Notice that the equation must balance in terms of the ratio of the ions. In this case there are 2 nitrate ions for each magnesium ion. Notice also that the total of (+ve) charges is the same as the total of (-ve) charges. Dissolving of aluminium chloride: Al2Cl3(s) 2Al+3(aq) + 3Cl-(aq)

Ions dissolve from the lattice into solution, while dissolved ions leave the solution and join the lattice AT THE SAME RATE
This ion dissolves

Try the Worksheet at the end of this section Dilute, Concentrated, Saturated
If you dissolved a pinch of salt in a bucket of water this is a dilute solution, meaning that it contains very little solute compared to the amount of solvent. If you dissolved a heaped spoonful of salt in a glass of water the solution is concentrated... it has quite a lot of solute compared to the amount of solvent. There is a limit to how much solute can be dissolved in a given amount of solvent. When this limit is reached, and the solution contains as much solute as it can hold, it is said to be saturated. Different compounds have different solubilities, and this o can change with temperature, but as an example, at 25 C a salt-water solution is saturated when about 36g of salt have dissolved in each 100mL of water. We say the solubility of salt is 36 g/100mL, or simply 36 % m/v. (% m/v means percentage mass to volume and refers to the measurement of grams (mass) in 100mL (volume). This is not the only way we can measure the concentration of a solution... the Mole is Back!! (soon)
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Undissolved solid

Since dissolving and precipitating occur at the same rate, the concentration of the solution does not change, and the amount of undissolved solid remains the same. At the macroscopic level, it seems that nothing is happening, but down at the atomic level things are moving... ions constantly dissolving into solution and precipitating back out of it again. This is known as a Dynamic Equilibrium Dynamic Equilibrium in a saturated salt solution: NaCl(s) Na+(aq) + Cl-(aq)

This double-arrow symbol indicates that the reaction is occurring in both directions, at the same rate, in dynamic equilibrium. Many chemical reactions reach this state.

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Precipitation Reactions
Not all ionic compounds are as soluble as salt. Some reach saturation at such a low concentration that you can consider them as being insoluble. Silver nitrate (AgNO3) is soluble: AgNO3(s) Sodium chloride is soluble: NaCl(s) Na+(aq) + Cl-(aq) You may have done experimental work as suggested by this photo, to discover any patterns regarding which ions are often involved in precipitation reactions, and which mostly stay in solution. The results of such experiments are often summarized by a list of Solubility Rules. In keeping with the K.I.S.S. Principle, here is a simplified version: Ag+(aq) + NO3 (aq)
-

Ionic Solutions in dropper bottles Spot-T Test Plate

If you mix these 2 solutions together, you are really mixing water containing 4 separate ions... Na+, Cl-, Ag+ & NO3 . However, silver chloride (AgCl) has an extremely low solubility, so the mixture of ions may contain Ag+ ions and Cl- ions at concentrations way above the saturation concentration of AgCl. The ions will immediately form an ionic crystal lattice and solid AgCl will precipitate from the solution, until the correct dynamic equilibrium of solid and solution is re-established. Precipitation of solid silver chloride:
Na+(aq)+ Cl-(aq) + Ag+(aq) + NO3 (aq)
-

Solubility Rules
Mostly Soluble (and stay in solution)

AgCl(s) + Na+(aq) + NO3 (aq)

Na+ & K+ always

NO3 always

Cl- Br- & I- (except with Ag+ & Pb+2)


This is an ionic equation describing exactly what happened. On the left is the mixture of ions that were brought together in the 2 solutions. The Ag+ and Cl- ions have combined to form solid AgCl, while the other 2 ions have stayed in solution, unchanged... they are spectators. We can leave out the spectators to see the essential change that occurred:
Cl-(aq) + Ag+(aq) AgCl(s)

SO4

-2

(except with Ag+ Pb+2 & Ba+2)

Mostly Insoluble ( and form precipitates)

CO3

-2

(except with Na+ & K+)

OH- (except with Na+ K+ Ba+2 Ca+2)


If you learn these rules you can predict what will happen when 2 ionic solutions are mixed: Example 1 Mix solutions of barium hydroxide & potassium iodide. Prediction: No reaction. There is no combination of any of these ions which will form an insoluble precipitate. Example 2 Mix solutions of potassium carbonate with copper(II) sulfate. Prediction: A precipitate of copper(II) carbonate will form. Net ionic equation: -2 Cu+2(aq) + CO3 (aq) CuCO3(s)

This is a net ionic equation. Notice that it is simply the reverse of the equation for the dissolving of silver chloride. Ionic equations can be tricky to balance. If insoluble PbCl2 is formed by precipitation of ions, the net ionic equation is:
2 Cl-(aq) + Pb+2(aq) PbCl2(s)

Notice that 2 Cl- ions are needed. If these were delivered in a sodium chloride solution, then to balance everything, 2 Na+ ions must be present in the full ionic equation.
2Na+(aq)+ 2Cl-(aq)+ Pb+2(aq)+ 2NO3 (aq)
-

PbCl2(s) + 2Na+(aq) + 2NO3 (aq)

Try the Worksheet at the end of the Section


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Measuring Concentrations With the Mole


Earlier, the idea of measuring the concentration of a solution was introduced. One way to do this is to measure the mass of solute in each 100mL of solution (%m/v). However, although this is fairly common, it is not the standard way to express or measure concentrations. The Mole is Back! For reasons that will become obvious later, the standard method for measuring concentrations of solutions is in moles per litre (molL-1). Concentration = number of moles (of solute) (of solution) Volume (of solution) c= n V Units of measurement c in moles per litre (molL-1) n in moles (mol), and remember that n = m V in litres (L) MM

Why are There Different Concentration Measurements?


Simple: its a matter of convenience, for the particular task being done. In an industrial situation it might be required to mix up a salt solution for pickling olives (for example). To make it easy and efficient, the instructions might be 1 kg of salt to every 10 litres of water or some such. In this case the units of concentration would be kilograms per litre (kgL-1). In another situation, it might be convenient to use %m/v. In Chemistry, it is usually best to measure in molL-1 (molarity) because this allows easy conversions of mass, volumes of gases and volumes of solutions, when chemical reactions are involved.

Technique For Making Solutions


One important laboratory technique is that of making up a solution to a required concentration. The first step is to calculate the mass of solute required to make the desired solution, as in Example Problem 2, on the left of this page. Once this exact mass is weighed out, the technique is:

Example Problem 1 If 12.00g of pure solid NaCl was dissolved in water, and made up to 250.0mL (0.2500 L) of solution, what is the molar concentration (molarity) of the solution? Solution: Step 1. Find the number of moles. MM(NaCl) = 58.44g n = m/MM = 12.00/58.44 = 0.2053 mol Step 2. Calculate concentration. c = n/V = 0.2053/0.2500 concentration = 0.8214 molL-1 Example Problem 2 What mass of potassium iodide is required to prepare 150.0mL (0.1500 L) of solution with a concentration of 0.2000 molL-1? Step 1. How many moles are required to get this concentration? c = n/V so n = cV = 0.2000 x 0.1500 = 0.03000 mol Step 2. What mass is this? MM(KI) = 166.0g n = m/MM, so m = n x MM = 0.03000 x 166.0 mass = 4.980g

Dissolve Solute in a small amount of (pure) water in a clean beaker

Volumetric Flask

Carefully transfer solution into a Volumetric Flask. Rinse beaker with small amounts of water & add washings to flask

Add water to flask to fill it to the mark. (Use a dropper to avoid overshooting) Insert stopper & mix well.

Note that to make 500mL of solution you do NOT add 500mL of water. You make the volume of the solution up to 500mL... yes, there IS a difference! Once a solution is prepared this way, other solutions can be made from it by taking measured quantities, and diluting them appropriately. 14 www.keepitsimplescience.com.au

Try the Worksheet, at the end of Section


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Diluting to a Desired Concentration


A common procedure in the Chemistry laboratory is to have chemical solutions already prepared to a known concentration, and dilute them to new concentrations as needed. To calculate the new concentration, or to calculate the volume needed to get a desired concentration, use the following relationship:

Equipment for Diluting Solutions You may have done practical work in the laboratory to learn how to carry out a dilution. The required volume (calculated as in Example Problem 2 on the left) is measured by pipette and transferred to a volumetric flask. Pure water is added to the mark.

c1V1 = c2V2
(or cV = constant) c1 = concentration of original solution, in molL-1 V1 = volume of original solution used, in L ** c2 = concentration of diluted solution, in molL-1 V2 = volume of diluted solution made, in L ** ** It actually doesnt matter what units you use, so long as you are consistent throughout the calculation. In the examples below, volumes are in mL.

These are bulb pipettes which measure accurately a single volume e.g. 25.00mL For odd amounts (like 5.6mL) use a graduated pipette.
Bulb Pipettes

The Concentration of Ions in Solution


Example Problem 1 If 25.00mL of a solution of concentration 0.3750molL-1 was diluted to a new volume of 500.0mL, what is the concentration of the diluted solution? Solution c1V1 = c2V2, so c2 = c1V1/V2 = 0.3750 x 25.00/500.0 c2 = 0.01875 molL-1 (1.875 x 10-2) When an ionic compound dissolves in water the ionic lattice disintegrates as the individual ions are hydrated and taken into the solution. What is the concentration of the individual ions? If the compound contains ions in a 1:1 ratio this is a very simple situation. For example, consider the dissolving of salt, sodium chloride: NaCl(s) Na+(aq) + Cl-(aq)

Example Problem 2 It is required to make 250.0mL of a solution with concentration 5.000x10-3 molL-1, from a stock solution with concentration 0.2250molL-1. What volume of the stock solution should be measured for dilution? Solution c1V1 = c2V2, so V1 = c2V2/c1 = 5.000x10-3 x 250.0/0.2250 V1 = 5.555 mL (In fact, you would not be able to measure such a precise volume by pipette. Appropriate answer is really 5.6 mL)

If the solution has a concentration of (say) 0.5 molL-1, then the concentration of the Na+ ions is 0.5 molL-1 and the concentration of the Cl- ions is 0.5 molL-1 as well. However, if magnesium chloride (MgCl2)dissolves there are 2 chloride ions for every 1 magnesium ion. If the concentration of the solution was 0.5 molL-1, then the individual ion concentrations are: MgCl2(s) Mg+2(aq) + 2Cl-(aq) 0.5 molL-1 0.5 molL-1 1.0 molL-1

In a 0.5 molL-1 solution of aluminium sulfate the concentrations would be: -2 Al2(SO4)3(s) 2Al+3(aq) + 3SO4 (aq) 0.5 molL-1 1.0 molL-1 1.5 molL-1

Try the Worksheet, at the end of Section

Something worth knowing: In Chemistry, square brackets around a formula is shorthand for molar concentration of... e.g. [NaCl] means molar concentration of NaCl 15 www.keepitsimplescience.com.au

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Mass, Volume & Concentration in Precipitation Reactions


Armed with a knowledge of molarity you can now link calculations involving concentration of solutions to masses and even gas volume quantities.

Example Problem 1 15.00mL of 0.3055 molL-1 solution of lead(II) nitrate was treated as follows: An excess of potassium iodide solution was added, causing a precipitate. The solid precipitate was collected by filtration, dried and then weighed. What substance, and what mass, was collected? (Note: an excess of something means that the quantity added was more than enough to ensure a complete reaction) Solution Step 1: use the Solubility Rules to figure out what substance precipitated, then write a balanced equation for the reaction. Pb(NO3)2(aq) + 2KI(aq) PbI2(s) + 2KNO3(aq)

Example Problem 2 To measure the concentration of salt in a 40.0mL seawater sample, an excess of silver nitrate solution was added to precipitate all the chloride ions. The precipitate was collected by filtration, dried and weighed. Its mass was 2.76g a) What substance was precipitated? b) Write a net ionic equation for the precipitation. c) Write a full ionic equation for the reaction. d) Calculate the number of moles of precipitate collected. e) How many moles of chloride ions must have been in the seawater sample? f) Calculate the molar concentration of salt in the seawater. Solution a) From Solubility Rules: Silver chloride, AgCl b) Ag+(aq) + Cl-(aq)
-

Step 2: find how many moles of Pb(NO3)2 were present in the 15mL (0.015 L) of solution. c = n/V, so n = cV = 0.3055 x 0.01500 n(Pb(NO3)2) = 4.5825 x 10-3 mol Step 3: find how many moles of PbI2 were precipitated. The balanced equation shows the mole ratio is 1:1, so n(PbI2) = 4.5825 x 10-3 mol Step 4: convert moles to mass. MM(PbI2) = 461.0g n = m/MM, so m = n x MM -3 = 4.5825x10 x 461.0 m(PbI2) = 2.113g Note: The working above assumes 100% precipitation of the lead ions. Technically, a small fraction of the lead ions would stay in the solution, so not quite all of it would precipitate. However, the solubility of PbI2 is very low, so for simplicity (K.I.S.S.) were assuming complete precipitation. Example Problem 3 A little revision of Topic 2 What volume of hydrogen gas (measured at SLC) could be produced from the complete reaction of 50.0mL of 1.50 molL-1 hydrochloric acid with magnesium. Solution As usual, start with a balanced equation: Mg(s) + 2HCl(aq) H2(g) + MgCl2(aq)
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AgCl(s)

c) Ag+(aq)+ NO3 (aq)+ Na+(aq)+ Cl-(aq) AgCl(s)+ NO3 (aq)+ Na+(aq) d) n = m/MM = 2.76 / 143.35 n(AgCl) = 0.0193 mol MM(AgCl) = 143.35g
-

e) Mole ratio in equation is 1:1 n(Cl-) = 0.0193 mol f) c = n/V = 0.0193 / 0.040 c(NaCl) = 0.481 molL-1 (40mL = 0.040 L)

Worksheet next page


Moles of HCl present in the solution: c = n/V, so n(HCl) = cV = 1.50 x 0.050 = 0.075 mol Moles of H2: equation shows mole ratio = 2:1 n(H2) = 0.075/2 = 0.0375 mol Volume of H2: (remember 1 mole = 24.8 L at SLC) vol(H2) = 0.0375 x 24.8 = 0.930 L (930 mL) 16 www.keepitsimplescience.com.au

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Worksheet 3
Practice Problems 1. Ionic Equations for Dissolving Write ionic equations (showing states) for the dissolving of each compound in water. a) potassium bromide b) calcium sulfate c) lithium nitrate d) magnesium iodide e) aluminium nitrate f) ammonium chloride g) iron(II) nitrate h) copper (II) sulfate i) calcium hydroxide 2. Predicting Precipitates Use the Solubility Rules to predict the result of mixing each pair of ionic solutions. To answer, write No Reaction, or name the compound which would form a solid precipitate. a) sodium sulfate & barium nitrate b) potassium hydroxide & iron(II) chloride c) calcium sulfate & sodium hydroxide d) lead(II) nitrate & potassium chloride e) magnesium bromide & silver nitrate f) potassium chloride & sodium carbonate g) sodium carbonate & magnesium chloride h) copper(II) sulfate & sodium carbonate i) barium nitrate & copper(II) sulfate 3. Ionic Equations For each of the combinations in Q2 which would react to form precipitates: i) write the full ionic equation, and balance. ii) write the net ionic equation 4. Molarity Calculations a) What is the molarity of a solution if: i) 2.50 mol is dissolved in 0.750 L of solution? ii) 0.025 mol is dissolved in 0.050 L of solution? iii) 0.35 mol is dissolved in 100 mL of solution? iv) 1.2x10-3mol is dissolved in 4.0 L of solution? v) 0.95 mol is dissolved in 200mL of solution? b) How many moles of solute are in i) 2.00 L of a 0.400 molL-1 solution? ii) 0.450 L of a 1.25 molL-1 solution? iii) 50mL of a 0.025 molL-1 solution? iv) 2.00mL of a 0.0035 molL-1 solution? v) 0.050 L of a 2.25 molL-1 solution?

5. Molarity & Mass Calculations a) What is the molar concentration of each solution? Mass of solute dissolved in i) 15.80g of potassium nitrate ii) 3.66g of copper(II) sulfate iii) 127g of sodium chloride iv) 85.6g of lead(II) nitrate v) 2.35g of lithium bromide Volume of Solution 0.200 L 500mL 1.50 L 3,000mL 250mL

b) What mass of solute is required to make each solution? Solute Concentration (molL-1) Volume i) aluminium chloride 0.028 0.050 L ii) sodium sulfate 0.400 250 mL iii) calcium hydroxide 3.75x10-5 2.50 L iv) potassium bromide 1.50 25.0 mL v) copper(II) nitrate 0.800 100 mL 6. Dilution of Solutions a) What is the concentration of the diluted solution if: i) 25.0 mL of 0.100 MolL-1 solution was diluted to 1.00L? ii) 5.00 mL of 1.25 MolL-1 solution was diluted to 100mL? iii) 2.5 mL of 0.025 MolL-1 solution was diluted to 0.50L? iv) 8.6 mL of 0.500 MolL-1 solution was diluted to 50mL? v) 10.0mL of 5.35x10-3 MolL-1 sol. was diluted to 250mL? b) In each case, what volume of the stock solution is needed to make up the given volume at the required concentration? Stock Solution Volume Concentration -1 Required Required (molL-1) (molL ) i) 1.50 1.00L 0.250 ii) 6.00 100mL 0.500 iii) 0.250 250mL 1.00x10-4 iv) 0.500 50mL 0.010 v) 0.875 10.0mL 0.500 7. Mass & Concentration in Precipitation Reactions a) An excess of sodium sulfate solution was added to 25.0mL of a 0.500 molL-1 solution of barium nitrate. Assuming complete precipitation, calculate the mass of dried precipitate which could be collected. b) The same reaction as in (a) was used to analyse the concentration of a solution of sodium sulfate. A 10.0mL sample of the solution was taken, and an excess of barium nitrate solution was added. The mass of dried precipitate collected was 1.27g. What was the concentration of the sodium sulfate solution? c) A precipitate of silver carbonate was collected from 50.0mL of 0.500molL-1 solution of silver nitrate, by adding an excess of potassium carbonate solution. i) Find the mass of dried silver carbonate collected. ii) (Some Revision!) If this silver carbonate was heated and decomposed, what mass of silver metal, and what volume of carbon dioxide gas (at SLC) would be formed?

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4. HEAT CAPACITY & CALORIMETRY


Temperature, Heat Energy & Heat Capacity
When heat is added to any substance, what really happens is that the particles (atoms/ions/molecules) move faster. In solids the particles just vibrate more quickly, in liquids or gases they actually move around faster. What we measure and understand as temperature is really a measurement of the average kinetic energy (movement) of the particles. Not all particles speed up equally when heat is added:
100 grams of Copper

Measuring Heat Energy Changes


When any substance gains or loses heat, the amount of heat energy involved depends upon: the amount of substance. i.e the mass. the Specific Heat Capacity of that substance. the temperature change.

H = - m C T
H = change in heat energy, in joules (J) m = mass of substance, in grams (g) C = Specific Heat Capacity, in J/oC/g T = temperature change, in degrees celsius (oC) Notes The Greek letter delta () means change in... Chemical Data Sheets may give Heat Capacities for 1 kilogram of substance instead of 1 gram. No problem; just divide by 1,000. Why is there a negative sign?? For technical reasons (explained later) if the temperature goes up, the energy change is considered negative. If temperature drops (negative temp. rise), the energy change is considered positive. The negative sign in the equation takes care of this. Example Problem 1 How much energy is needed to raise the temperature of 50.0g of water by 12.0oC? Specific Heat Capacity of water = 4.18 J/oC/g Solution H = - mCT = - 50.0 x 4.18 x 12.0 = - 2,508 J (In this non-chemical situation the (-ve) sign can really be ignored. The energy required is 2.51 x 103 J (2.51 kJ)) Example Problem 2 If 10,000 J of heat energy was added to 100g of ethanol (Specific Heat Capacity = 2.44 J/oC/g) what would be the temperature rise? Solution Since the temperature will rise, technically the energy is a negative quantity, so H = - 10,000J H = - mCT, so T = H/(-m x C) = -10,000/(-100 x 2.44) = 41.0 oC i.e. Temp. will rise by 41oC

1000 joules of Heat Energy

Temperature rise about 25oC

If you do the same thing to water:


100 grams of Water

1000 joules of Heat Energy

Temperature rise about 2oC

The temperature of the water does not change much when heat is added. (Explanation: its those sticky polar molecules again! Water molecules cling to each other by hydrogen bonding. This means they are hard to accelerate, and it takes more energy to make them speed up.) Specific Heat Capacity is a measure of how much heat energy (in joules) is required to change the temperature of 1 gram of a substance, by 1oC. The units of Heat Capacity are, therefore, joules per degree per gram (J/oC/g) Comparison of Some Specific Heat Capacities Substance Water Typical Metal Other Liquid Solvents Ethanol (alcohol) Acetone Petrol (mixture) Heat Capacity (J/ C/g) 4.18 0.3 (approx) 2.44 2.17 2.2 (approx)
o

Note that waters Heat Capacity is much higher than most other substances... ...another of waters weird and unusual properties
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Try the Worksheet at End of Section


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Calorimetry

Endothermic and Exothermic Changes


Exothermic Reactions (Exo= to go out) are the reactions that produce and release energy.
Reactants Energy Level Energy Content Energy released by chemicals during reaction

is a technique used to measure the energy change occurring during chemical processes. The word is derived from the calorie, a unit for heat energy no longer in use. The equipment used to make energy measurements is called a calorimeter. (Since we now use joules for our energy unit, maybe we should call it a joulemeter) Since many chemical processes occur in water, and because water has such a high Specific Heat Capacity (i.e. it can absorb lots of energy with little temperature change) calorimetry often uses water as the working fluid or medium used to absorb the heat energy. Simple Laboratory Calorimeter Thermometer measures temperature change

were introduced in Topic 1. Here is a quick reminder:

= H

negative

Products have LESS energy

The amount of energy involved is the delta-H for the process, and is measured per mole of the substance(s) involved. When the chemicals lose energy, the temperature in a calorimeter rises, because the energy release heats up the water in the calorimeter. This is why, when the temperature rises, the energy quantity is considered negative... the chemicals involved have LOST this amount of heat energy. Endothermic Reactions (Endo = to go in) are the reactions that absorb energy... those where you must supply energy to make it happen.
Products have MORE energy Energy Content Energy absorbed by chemicals during reaction Reactants Energy Level

Copper Beaker reaction container Polystyrene body and lid prevents heat loss/gain with the surroundings

= H

positive

The delta-H for this change is considered positive because the chemicals have gained energy. The temp. change is negative, because the calorimeter temp. drops.

Practical Work: Heat of Solution


You may have carried out experiments to measure the energy change that occurs when ionic compounds dissolve in water. General Method: Use a calorimeter to measure the temperature change in a measured mass of water, when a measured mass of a solid dissolves. You can then calculate: the energy change occurring (for the quantities used) and then, the energy change per gram of solute. and then, the energy change per mole of solute.
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Typical Results for dissolving of Potassium hydroxide Mass of water placed in calorimeter = 100g Mass of potassium hydroxide dissolved = 4.50g Initial temperature of water = 21oC Final temperature of solution, after dissolving = 28oC Temperature change, T = 7.0oC Calculations: Solution is mostly water H = - mCT = - (100 + 4.5) x 4.18 x 7.0 = - 3, 058 J for the dissolving of 4.50g Energy per gram: H = - 3,058/4.50 = -679 J per gram Energy per mole: MM(KOH) = 56.1g H = -679 x 56.1 = - 38,100 J per mole Heat of Solution = - 38.1 kJmol-1 (exothermic) 19 www.keepitsimplescience.com.au
Total mass in calorimeter

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Heat of Solution

Waters Heat Capacity & Life on Earth


The fact that water has a remarkably high Specific Heat Capacity is of enormous significance to weather, climate and life on Earth. It means that, on a hot day, the ocean or a lake can absorb a large amount of energy from the Sun without much temperature change. The air and the land may get very hot, but the water temperature changes very little. In cold weather, the air and land can get really cold, but the water changes only a little. This means that water habitats have very stable temperatures and do not change much from day to night, or even summer to winter. Aquatic organisms do not need complex temperature control mechanisms because their habitat remains quite stable.

is the common name for the energy change that occurs when 1 mole of a solute dissolves in water. is negative if energy is released. (exothermic: the calorimeter temperature rises) Examples: soluble hydroxides (e.g. NaOH, KOH) is positive if energy is absorbed. (endothermic: the calorimeter temperature falls) Examples: ammonium nitrate (NH4NO3), ammonium chloride (NH4Cl)

Hsol Hsol

Limitations of Calorimetry

When you use a simple calorimeter to measure an energy change in the laboratory, there are a number of assumptions and approximations involved. It is assumed that the calorimeter itself does not absorb a significant amount of the heat energy of the reaction. This source of error is minimized by using a copper reaction vessel, since the very low Specific Heat Capacity of copper means it absorbs little energy. It is assumed that there is no heat lost or gained between the calorimeter and the surroundings. This source of error can be minimized by good heat insulation of the calorimeter. It is assumed that the Specific Heat Capacity of the solution reacting in the calorimeter is the same as water. i.e. C = 4.18 J/oC/g For many solutions this is not quite true, but (generally) the error this causes is very small. A serious limitation of many calorimetry experiments in school laboratories is the poor precision of the usual lab. thermometers. Usually these can only be read to the nearest 0.5oC, and if the temperature change is only a few degrees, the % error is huge. Serious calorimetry needs thermometers with a precision of at least 0.1oC.

More importantly, the oceans absorb and transport (via ocean currents) huge quantities of heat from the tropics towards the poles. This has the effect of cooling the tropical areas and warming the temperate regions, and generally evening-out the Earths temperature. Without water, very little of the Earth would have liveable temperatures. Without the moderating effect of water, the tropics would be too hot for life, and the temperate regions would be too cold.

Thermal Pollution
Some industries, especially coal-burning or nuclear power stations produce large amounts of waste heat. In some places, these plants are situateded beside lakes or the sea so that the water can be used for cooling the equipment. Typically, lake water is pumped through the equipment, then hot water discharged back into the lake.

This is thermal pollution, and is very destructive to aquatic habitats. The main problem is a matter of solubility. Oxygen, and other gases, are sparingly soluble in water. Aquatic organisms are totally dependent on this low concentration of dissolved gases for their survival. The problem is, that the solubility of gases decreases as the temperature rises. If the water temperature rises by as little as 5oC, the dissolved oxygen concentration drops by 20% and fish begin to suffocate. Not only that, but increased temperatures can interfer with the normal breeding cycles and alter the delicate balance between populations of food plants, disease microbes, parasites, etc. Habitat destroyed! 20 www.keepitsimplescience.com.au

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Worksheet 4
Part A Fill in the blanks Temperature is a measure of the average a)........................... energy of the particles within a substance. When heat is added, the particles b)............................................. However, some substances require more heat energy than others for the same temperature change. This difference is measured by the property of c)................................................................... which has units of d)............................... Water has a very e).................................. (high/low) value. The amount of heat energy involved in any change is given by the formula f)....................................... A g).................................... is a device for measuring energy changes. Water is often used as the working fluid because of its high h)................................................... Capacity. i)...................-thermic changes release energy, so the temperature in the calorimeter j).................................... The chemicals in the reaction have k).......................... energy, so the energy value is considered l)........................... (+/-) m)...................-thermic changes absorb energy, so the temperature in the calorimeter n).................................... The chemicals in the reaction have o).......................... energy, so the energy value is considered p)........................... (+/-) The energy change involved in dissolving a solution is called the q).............................................................................. Calorimetry has a number of limitations and sources of error; the calorimeter itself may r).................................................. This error is minimized by using a reaction container with a very low s)............................................................................. heat may be lost or gained between the calorimeter and the t)............................................ This error is minimized by u)............................................ the calorimeter. it is assumed that the reacting solution has the same v)....................................................................... as water. This is an approximation, but only causes a w)........................ error. Experimental error often comes from the lack of precision of the x)............................................ Waters very high S.H.C. is of great significance to the Earths y)..................................... and ................................... Water habitats have very z)...................................... temperatures, and the ocean currents aa)................................ huge amounts of heat, ab)...................................... the tropics and warming the ac)................................................ regions. Thermal pollution is the release of ad).................................... into aquatic habitats. This is destructive, mainly because the ae)................................ of gases (such as af).............................) becomes much ag)............................................... at higher temperatures.
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Part B Practice Problems 1. Simple Heat Calculations. (The +/- signs may be ignored) a) Calculate the amount of heat energy involved to:
o o i) heat 50.0g of water from 20 C to 50 C. o ii) cool 400g of water from 95 C to 10oC. iii) heat a swimming pool containing 560 tonnes of water (1 tonne = 1x106 gram) from 12oC to 28oC. iv) heat 100g of copper (C = 0.39 J/oC/g) from 10oC to its melting point, 1,085oC. v) cool a 100 kg car engine (steel, C = 0.45 J/oC/g) from o o 120 C to 20 C.

b) Calculate the Final Temperature (nearest degree) if:


o i) 250g of water at 20 C absorbs 72,000 J of heat. ii) 5.00 kJ of energy was extracted from 80.0g of water at 25oC. iii) 1 L of water (= 1kg mass) at 4oC absorbs 10,000J. iv) a 5.00kg lump of steel at -25oC absorbs 20,000J. v) 20.0g of ethanol (C = 2.44 J/oC/g) at 30oC loses 1.2kJ.

2. Heat of Solution Calculations (+/- sign important!) a) Find the Molar Heat of Solution if: i) when 5.85g of ammonium nitrate dissolved in 100mL of water (100mL water = 100g) in a calorimeter, the temperature went from 24oC to 11oC. ii) 8.42g of sodium carbonate was dissolved in 100mL of water in a calorimeter. The temperature increased by 9.5oC. b) Find the Final Temperature i) The heat of solution for sodium hydroxide is listed as Hsol (NaOH) = -41.6 kJmol-1. If 10.0g of NaOH was dissolved in enough water to make 250g of solution, what would the final temperature be? The initial temperature was 18oC. ii) The heat of solution for ammonium chloride is listed as Hsol (NH4Cl) = +15.2 kJmol-1. If 18.5g of NH4Cl was dissolved in 150mL of water (initially at 22oC) what would be the final temperature?

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CONCEPT DIAGRAM (Mind Map) OF TOPIC


Some students find that memorizing the OUTLINE of a topic helps them learn and remember the concepts and important facts. Practise on this blank version.

WATER

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Practice Questions

These are not intended to be "HSC style" questions, but to challenge your basic knowledge and understanding of the topic, and remind you of what you NEED to know at the K.I.S.S. Principle level. When you have confidently mastered this level, it is strongly recommended you work on questions from past exam papers. Part A Multiple Choice

7. If small, non-polar molecules were mixed with water, you would expect them to: A. dissolve, as separate hydrated ions. B. dissolve, hydrated by hydrogen bonding. C. dissolve, dispersed in water at low concentration. D. not dissolve at all. 8. The correct ionic equation for the dissolving of solid aluminium chloride is: A. AlCl3(s) AlCl3(aq) B. C. D. AlCl3(s) AlCl3(s) AlCl3(s) Al+3(aq) + Cl-(aq) Al+3(aq) + 3Cl-(aq) 3Al+(aq) + Cl-3(aq)

1. The water content of the lithosphere is mainly in the form of A. water vapour B. liquid water C. solid ice D. water of crystallization in minerals 2. The density anomaly of water is that: A. the density of ice is higher than liquid water. B. the density of water is exactly 1.00 g/mL. C. ice floats in water. D. waters density is extremely high. 3. The compound H2Se Se can be represented by H H the Lewis Formula shown. The covalent molecule contains 2 unshared pairs of electrons. You would expect its shape to be: A. linear B. tetrahedral C. triangular pyramid D. bent 4. The inter-molecular forces in water are really: A. hydrogen bonds B. polar covalent bonds C. pure covalent bonds D. ionic attractions 5. Hydrogen Bonds are likely to occur within substances in which hydrogen atoms are bonded to atoms of: A. oxygen, chlorine and carbon. B. nitrogen, oxygen and fluorine. C. sulfur, oxygen and chlorine. D. fluorine, chlorine and bromine. 6. Water tends to form droplets because of its: A. high viscosity. B. high surface tension. C. density anomaly D. high boiling point.

9. If solutions of potassium carbonate and calcium nitrate were mixed together, you would observe: A. no reaction. B. a precipitate of potassium nitrate. C. a precipitate of calcium carbonate. D. a precipitate of potassium calcide. 10. A saturated solution of lithium bromide is in the same beaker with solid crystals of lithium bromide. The concentration of ions in solution does not change over time because: A. the rates of dissolving and precipitating are the same. B. there can be no further dissolving because the solution is saturated. C. all chemical processes have ceased at equilibrium. D. the lithium & bromine ions are at equal concentrations. 11. The number of moles of sodium ions in 500mL of a 2.0 molL-1 salt solution, is the same as the number of moles of chloride ions in: -1 A. 500mL of a 2.0molL solution of MgCl2. -1 B. 1 L of a 1.0molL solution of MgCl2. C. 2 L of a 1.0molL-1 solution of MgCl2. D. 250mL of a 2.0molL-1 solution of MgCl2. 12. To make 2.0 L of potassium bromide solution to a concentration of 0.1 molL-1 would required a mass of KBr closest to: A. 2 g B. 10g C. 20 g D. 120g 13. In the process of accurately preparing 250mL of a solution to a specified concentration, you would need to accurately: A. measure 250.0mL by pipette. B. add water to the mark in a 250mL volumetric flask. C. fill a 250mL measuring cylinder. D. use a 250mL graduated beaker.

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14. The Specific Heat Capacity values for 4 substances are shown. Substance S.H.C.(J/oC/g) A 0.95 B 2.5 C 1.2 D 2.1 Which substance (A, B, C or D) would have the largest temperature rise, if equal amounts of heat energy were added to equal masses of each substance? 15. An exothermic process is considered to have a negative value for the energy change, because: A. the temperature in the reaction container drops. B. you need to put energy into the system. C. it is the opposite of an endothermic change. D. the chemicals have lost energy in the change. 16. Thermal Pollution damages ecosystems mainly because: A. living things cannot tolerate the temperature rise. B. less oxygen can dissolve in warmer water. C. the extra heat speeds up plant growth. D. more dirt dissolves in warm water, so erosion increases. Longer Response Questions Mark values shown are suggestions only, and are to give you an idea of how detailed an answer is appropriate. 17. (6 marks) List 2 important roles of water: a) in living things. b) as a factor in weather , climate and geography. c) as a resource for human civilization. 18. (4 marks) a) What is meant by saying that water has a density anomaly? b) Explain, in terms of bonding and particle arrangements, why water has a density anomaly. 19. (4 marks) a) Draw a Lewis Formula for the water molecule. b) Explain the shape of the molecule 20. (6 marks) The diagram represents 2 water molecules. a) Copy this diagram, then add labels to identify: i) a covalent bond. ii) a hydrogen bond. iii) the partial charges (+ , -) on one molecule. b) Explain what is meant by a polar covalent bond. c) Explain how the presence of hydrogen bonds is responsible for waters relatively high m.p. & b.p.

21. ( marks) a) What is meant by the viscosity of a liquid? b) Describe a laboratory exercise you have done to compare the viscosity of 2 or more different liquids. c) How does the viscosity of water compare to that of other liquids with similar sized molecules? d) Discuss the significance to aquatic animals, of your answer to part (c). 22. (6 marks) Write ionic equations to describe: a) the dissolving of calcium chloride in water. b) the precipitation of calcium chloride from water. (For example, if a solution was evaporated to dryness) c) the situation of a saturated solution of calcium chloride, in contact with solid calcium chloride. 23. (10 marks) a) Predict what would happen if solutions of potassium carbonate and lead(II) nitrate were mixed together. b) Write a full ionic equation to describe the reaction. c) The lead(II) nitrate solution had a concentration of 0.500 molL-1 and 20.0mL was used. Calculate the mass of precipitate formed. (Assume complete precipitation, after adding an excess of potassium carbonate solution.) d) Write a symbol equation to describe the decomposition of the dried precipitate, given that a pure metal is formed, and a mixture of 2 gases. e) Calculate the total gas volume (measured at SLC) formed by the decomposition of the quantity of precipitate formed in part (c). 24. (6 marks) You have been given the task of preparing 500mL of a solution of potassium iodide (KI) with a concentration of 0.250 molL-1, from the solid pure chemical. Describe the steps of the procedure, including the exact mass you would use, and any points of technique to ensure accuracy. 25. ( marks) Using a polystyrene cup as a simple calorimeter, a student added 50.0mL of water and measured its temperature to be 18oC. She weighed out 4.27g of lithium hydroxide and dissolved it in the water. The water temperature rose to a maximum of 45oC. a) Showing all working, calculate the molar Heat of Solution (including sign) for lithium hydroxide. b) Later, she looked up a Chemical Data Book and found the accepted value for Hsol(LiOH). It was a significantly larger amount of energy than the experimental results gave. Suggest 2 reasons why.

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