Chapter 5. Molecules and Compounds. Introductory Chemistry, 3 rd Edition Nivaldo Tro 2/21/2011

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Introductory Chemistry, 3 rd Edition Nivaldo Tro Chapter 5 Molecules and Compounds Based on notes of Roy Kennedy Massachusetts Bay Community College 2006, Prentice Hall Molecules and Compounds Salt Sodium shiny, reactive, poisonous Chlorine pale yellow gas, reactive, poisonous Sodium chloride table salt Sugar Carbon pencil or diamonds Hydrogen flammable gas Oxygen a gas in air Combine to form white crystalline sugar 1

Law of Constant Composition all pure substances have constant composition all samples of a pure substance contain the same elements in the same percentages (ratios) mixtures have variable composition Compounds Display Constant Composition If we decompose water by electrolysis, we find 16.0 grams of oxygen to every 2.00 grams of hydrogen. Water has a constant Mass Ratio of Oxygen to Hydrogen of 8.0. mass of oxygen Mass Ratio = mass of hydrogen = 16.0 g 2.0 g = 8.0 2

Why do Compounds Show Constant Composition the smallest piece of a compound is called a molecule every molecule of a compound has the same number and type of atoms since all the molecules of a compound are identical, every sample will have the same ratio of the elements since all molecules of a compound are identical, every sample of the compound will have the same properties Formulas Describe Compounds a compound is a distinct substance that is composed of atoms of two or more elements describe the compound by describing the number and type of each atom in the simplest unit of the compound molecules or ions each element represented by its letter symbol the number of atoms of each element is written to the right of the element as a subscript if there is only one atom, the 1 subscript is not written polyatomic groups are placed in parentheses if more than one 3

Formulas Describe Compounds water = H 2 O two atoms of hydrogen and 1 atom of oxygen table sugar = C 12 H 22 O 11 12 atoms of C, 22 atoms of H and 11 atoms O Order of Elements in a Formula metals written first NaCl nonmetals written in order from Table 5.1 CO 2 are occasional exceptions for historical or informational reasons H 2 O, but NaOH Table 5.1 Order of Listing Nonmetals in Chemical Formulas C P N H S I Br Cl O F Tro's Introductory Chemistry, Chapter 4 8 4

symbol of the polyatomic ion called nitrate Molecules with Polyatomic Ions symbol of the polyatomic ion called sulfate Mg(NO 3 ) 2 compound called magnesium nitrate implied 1 subscript on magnesium CaSO 4 compound called calcium sulfate implied 1 subscript on calcium parentheses to group two NO 3 s no parentheses for one SO 4 subscript indicating two NO 3 groups Molecules with Polyatomic Ions no subscript indicating one SO 4 group Mg(NO 3 ) 2 compound called magnesium nitrate implied 1 subscript on nitrogen, total 2 N stated 3 subscript on oxygen, total 6 O CaSO 4 compound called calcium sulfate implied 1 subscript on sulfur, total 1 S stated 4 subscript on oxygen, total 4 O 10 5

Classifying Materials atomic elements = elements whose particles are single atoms molecular elements = elements whose particles are multi-atom molecules molecular compounds = compounds whose particles are molecules made of only nonmetals ionic compounds = compounds whose particles are cations and anions Tro's Introductory Chemistry, Chapter 4 Molecular Elements Certain elements occur as 2 atom molecules Rule of 7 s there are 7 common diatomic elements find the element with atomic number 7, N make a figure 7 by going over to Group 7A, then down don t forget to include H 2 H 2 7 VIIA N 2 O 2 F 2 Cl2 Br 2 I 2 12 6

two or more nonmetals Molecular Compounds smallest unit is a molecule metals + nonmetals Ionic Compounds no individual molecule units, instead have a 3-dimensional array of cations and anions made of formula units 7

Molecular View of Elements and Compounds 15 Classify each of the following as either an atomic element, molecular element, molecular compound or ionic compound aluminum, Al aluminum chloride, AlCl 3 chlorine, Cl 2 acetone, C 3 H 6 O carbon monoxide, CO cobalt, Co 8

Classify each of the following as either an atomic element, molecular element, molecular compound or ionic compound aluminum, Al = atomic element aluminum chloride, AlCl 3 = ionic compound chlorine, Cl 2 = molecular element acetone, C 3 H 6 O = molecular compound carbon monoxide, CO = molecular compound cobalt, Co = atomic element Formula-to-Name Step 1 Is the compound one of the exceptions to the rules? 9

Common Names - Exceptions H 2 O = water, steam, ice NH 3 = ammonia CH 4 = methane NaCl = table salt C 12 H 22 O 11 = table sugar (and many more unfortunately!) Tro's Introductory Chemistry, Chapter 4 19 Formula-to-Name Step 2 What major class of compound is it? Ionic or Molecular 10

Major Classes Ionic metal + nonmetal metal first in formula Binary Ionic compounds with polyatomic ions Molecular 2 nonmetals Binary Molecular (or Binary Covalent) Acids formula starts with H though acids are molecular, they behave as ionic when dissolved in water may be binary or oxyacid Tro's Introductory Chemistry, Chapter 4 21 Formula-to-Name Step 3 What major subclass of compound is it? Binary Ionic, Ionic with Polyatomic Ions, Binary Molecular, Binary Acid, Oxyacid 11

Classifying Compounds Compounds containing a metal and a nonmetal = binary ionic Type I and II Compounds containing a polyatomic ion = ionic with polyatomic ion Compounds containing two nonmetals = binary molecular compounds Compounds containing H and a nonmetal = binary acids Compounds containing H and a polyatomic ion = oxyacids Tro's Introductory Chemistry, Chapter 4 23 Formula-to-Name Step 4 Apply Rules for the Class and Subclass 12

Formula-to-Name Rules for Ionic Made of cation and anion Name by simply naming the ions If cation is: Type I metal = metal name Type II metal = metal name(charge) Polyatomic ion = name of polyatomic ion If anion is: Nonmetal = stem of nonmetal name + ide Polyatomic ion = name of polyatomic ion Tro's Introductory Chemistry, Chapter 4 25 Monatomic Nonmetal Anion determine the charge from position on the Periodic Table to name anion, change ending on the element name to ide 4A = -4 5A = -3 6A = -2 7A = -1 C = carbide N = nitride O = oxide F = fluoride Si = silicide P = phosphide S = sulfide Cl = chloride Tro's Introductory Chemistry, Chapter 4 26 13

Metal Cations Type I metals whose ions can only have one possible charge IA, IIA, (Al, Ga, In) determine charge by position on the Periodic Table IA = +1, IIA = +2, (Al, Ga, In = +3) Type II metals whose ions can have more than one possible charge determine charge by charge on anion How do you know a metal cation is Type II? its not Type I!!! Tro's Introductory Chemistry, Chapter 4 27 Determine if the following metals are Type I or Type II. If Type I, determine the charge on the cation it forms. lithium, Li copper, Cu gallium, Ga tin, Sn strontium, Sr Tro's Introductory Chemistry, Chapter 4 28 14

Determine if the following metals are Type I or Type II. If Type I, determine the charge on the cation it forms. lithium, Li Type I +1 copper, Cu Type II gallium, Ga Type I +3 tin, Sn Type II strontium, Sr Type I +2 Tro's Introductory Chemistry, Chapter 4 29 Type I Binary Ionic Compounds Contain Metal Cation + Nonmetal Anion Metal listed first in formula & name 1. name metal cation first, name nonmetal anion second 2. cation name is the metal name 3. nonmetal anion named by changing the ending on the nonmetal name to -ide 30 15

Example Naming Binary Ionic, Type I Metal CsF 1. Is it one of the common exceptions? H 2 O, NH 3, CH 4, NaCl, C 12 H 22 O 11 = No! 2. Identify Major Class Cs = is a metal because it is on the left side of the PT F = is a nonmetal because it is on the right side of the PT Ionic 3. Identify the Subclass 2 elements, Binary Ionic 4. Is the metal Type I or Type II Cs is in Group IA, Type I Tro's Introductory Chemistry, Chapter 4 31 Example Naming Binary Ionic, Type I Metal CsF 5. Identify cation and anion Cs = Cs + because it is Group 1 F = F - because it is Group 7 6. Name the cation Cs + = cesium 7. Name the anion F - = fluoride 8. Write the cation name first, then the anion name cesium fluoride Tro's Introductory Chemistry, Chapter 4 32 16

Type II Binary Ionic Compounds Contain Metal Cation + Nonmetal Anion Metal listed first in formula & name 1. name metal cation first, name nonmetal anion second 2. metal cation name is the metal name followed by a Roman Numeral in parentheses to indicate its charge determine charge from anion charge Common Type II cations in Table 5.5 3. nonmetal anion named by changing the ending on the nonmetal name to -ide 33 Example Naming Binary Ionic, Type II Metal CuCl 1. Is it one of the common exceptions? H 2 O, NH 3, CH 4, NaCl, C 12 H 22 O 11 = No! 2. Identify Major Class Cu = is a metal because it is on the left side of the PT Cl = is a nonmetal because it is on the right side of the PT Ionic 3. Identify the Subclass 2 elements, Binary Ionic 4. Is the metal Type I or Type II Cu is not in Group IA, IIA, or (Al, Ga, In) Type II Tro's Introductory Chemistry, Chapter 4 34 17

Example Naming Binary Ionic, Type II Metal CuCl 5. Identify cation and anion Cl = Cl - because it is Group 7 Cu = Cu + to balance the charge 6. Name the cation Cu + = copper(i) 7. Name the anion Cl - = chloride 8. Write the cation name first, then the anion name copper(i) chloride Tro's Introductory Chemistry, Chapter 4 35 TiCl 4 Practice Name the Following Compounds. PbBr 2 Fe 2 S 3 18

Practice Name the Following Compounds, Continued. TiCl 4 Titanium(IV) chloride. Cl = 4( 1) = 4 Ti = +4 = 1(4+) PbBr 2 Lead(II) bromide. Br = 2( 1) = 2 Pb = +2 = 1(2+) Fe 2 S 3 Iron(III) sulfide. S = 3( 2) = 6 Pb = +6 = 2(3+) Compounds Containing Polyatomic Ions Polyatomic ions are single ions that contain more than one atom Name any ionic compound by naming cation first and then anion Non-polyatomic cations named like Type I and II Non-polyatomic anions named with -ide Tro's Introductory Chemistry, Chapter 4 38 19

Name Some Common Polyatomic Ions Formula acetate C 2 H 3 O 2 carbonate CO 3 2 hydrogen carbonate (aka bicarbonate) HCO 3 hydroxide OH nitrate NO 3 nitrite NO 2 chromate CrO 4 2 dichromate Cr 2 O 7 2 ammonium NH 4 + Name Tro's Introductory Chemistry, Chapter 4 hypochlorite ClO Formula chlorite ClO 2 chlorate ClO 3 perchlorate ClO 4 sulfate SO 4 2 sulfite SO 3 2 hydrogensulfate (aka bisulfate) hydrogensulfite (aka bisulfite) HSO 4 HSO 3 39 Patterns for Polyatomic Ions 1. elements in the same column form similar polyatomic ions same number of O s and same charge ClO 3- = chlorate BrO 3- = bromate 2. if the polyatomic ion starts with H, the name adds hydrogen- prefix before name and add 1 to the charge CO 3 2- = carbonate HCO 3-1 = hydrogencarbonate Tro's Introductory Chemistry, Chapter 4 40 20

Periodic Pattern of Polyatomic Ions -ate groups IIIA IVA VA VIA VIIA -3-2 -1 BO 3 CO 3 NO 3-2 -3-2 -1 SiO 3 PO 4 SO 4 ClO 3 AsO 4-3 SeO 4-2 TeO 4-2 BrO 3-1 IO 3-1 Tro's Introductory Chemistry, Chapter 4 41 Patterns for Polyatomic Ions -ate ion chlorate = ClO 3-1 -ate ion + 1 O same charge, per- prefix perchlorate = ClO 4-1 -ate ion 1 O same charge, -ite suffix chlorite = ClO 2-1 -ate ion 2 O same charge, hypo- prefix, -ite suffix hypochlorite = ClO -1 Tro's Introductory Chemistry, Chapter 4 42 21

Example Naming Ionic with Polyatomic Ion Fe(NO 3 ) 3 1. Is it one of the common exceptions? H 2 O, NH 3, CH 4, NaCl, C 12 H 22 O 11 = No! 2. Identify Major Class Fe = is a metal because it is on the left side of the PT NO 3 = is a polyatomic ion because it is in ( ) Ionic 3. Identify the Subclass there are 3 elements Ionic with Polyatomic Ion 4. Is the metal Type I or Type II Fe is not in Group IA, IIA, or (Al, Ga, In) Type II Tro's Introductory Chemistry, Chapter 4 43 Example Naming Ionic with Polyatomic Ion Fe(NO 3 ) 3 5. Identify the ions NO 3 = NO 3- a polyatomic ion Fe = Fe +3 to balance the charge of the 3 NO 3-1 6. Name the cation Fe +3 = iron(iii) (Type II) 7. Name the anion NO 3- = nitrate 8. Write the name of the cation followed by the name of the anion iron(iii) nitrate Tro's Introductory Chemistry, Chapter 4 44 22

1. NH 4 Cl Practice Name the Following 2. Ca(C 2 H 3 O 2 ) 2 3. Cu(NO 3 ) 2 Practice Name the Following, Continued 1. NH 4 Cl Ammonium chloride. 2. Ca(C 2 H 3 O 2 ) 2 Calcium acetate. 3. Cu(NO 3 ) 2 Copper(II) nitrate. NO 3 = 2( 1) = 2 Cu = +2 = 1(2+) 23

Binary Molecular Compounds of Two Nonmetals 1. Name first element in formula first. Use the full name of the element. 2. Name the second element in the formula with an ide, as if it were an anion. However, remember these compounds do not contain ions! 3. Use a prefix in front of each name to indicate the number of atoms. Never use the prefix mono- on the first element. Subscript Prefixes 1 = mono- Not used on first nonmetal. 2 = di- 3 = tri- 4 = tetra- 5 = penta- 6 = hexa- 7 = hepta- 8 = octa- Drop last a if name begins with vowel. 24

Example Naming Binary Molecular, BF 3 1. Is it one of the common exceptions? H 2 O, NH 3, CH 4, NaCl, C 12 H 22 O 11 = No! 2. Identify major class. B is a nonmetal because it is on the right side of the periodic table. F is a nonmetal because it is on the right side of the periodic table. Molecular. 3. Identify the subclass. 2 elements, Binary molecular. Example Naming Binary Molecular, BF 3, Continued 4. Name the first element. boron. 5. Name the second element with an ide. Fluorine fluoride. 6. Add a prefix to each name to indicate the subscript. monoboron, trifluoride. 7. Write the first element with prefix, then the second element with prefix. Drop prefix mono- from first element. boron trifluoride. 50 25

Practice Name the Following NO 2 PCl 5 I 2 F 7 Practice Name the Following Continued NO 2 Nitrogen dioxide. PCl 5 Phosphorus pentachloride. I 2 F 7 Diiodine heptafluoride. 26

Acids Acids are molecular compounds that form H + when dissolved in water. To indicate the compound is dissolved in water, (aq) is written after the formula. Not named as acid if not dissolved in water. Sour taste. Dissolve many metals. Like Zn, Fe, Mg, but not Au, Ag, Pt. Formula generally starts with H. E.g., HCl, H 2 SO 4. Acids, Continued Contain H +1 cation and anion. In aqueous solution. Binary acids have H +1 cation and nonmetal anion. Oxyacids have H +1 cation and polyatomic anion. 27

Naming Binary Acids Write a hydro- prefix. Follow with the nonmetal name. Change ending on nonmetal name to ic. Write the word acid at the end of the name. Example Naming Binary Acids, HCl 1. Is it one of the common exceptions? H 2 O, NH 3, CH 4, NaCl, C 12 H 22 O 11 = No! 2. Identify major class. 3. Identify the subclass. First element listed is H, Acid. 2 elements, Binary acid. 28

Example Naming Binary Acids, HCl, Continued 4. Identify the anion. Cl = Cl, chloride because Group 7A. 5. Name the anion with an ic suffix. Cl = chloride chloric 6. Add a hydro- prefix to the anion name. hydrochloric 7. Add the word acid to the end. hydrochloric acid Naming Oxyacids If polyatomic ion name ends in ate, then change ending to ic suffix. If polyatomic ion name ends in ite, then change ending to ous suffix. Write word acid at end of all names. 29

Example Naming Oxyacids, H 2 SO 4 1. Is it one of the common exceptions? H 2 O, NH 3, CH 4, NaCl, C 12 H 22 O 11 = No! 2. Identify major class. 3. Identify the subclass. First element listed is H, Acid. 3 elements in the formula, Oxyacid. Example Naming Oxyacids, H 2 SO 4,Continued 4. Identify the anion. SO 4 = SO 4 2- = sulfate. 5. If the anion has ate suffix, change it to ic. If the anion has ite suffix, change it to ous. SO 4 2- = sulfate sulfuric. 6. Write the name of the anion followed by the word acid. sulfuric acid (This is kind of an exception, to make it sound nicer!) 30

Example Naming Oxyacids, H 2 SO 3 1. Is it one of the common exceptions? H 2 O, NH 3, CH 4, NaCl, C 12 H 22 O 11 = No! 2. Identify major class. 3. Identify the subclass. First element listed is H, Acid. 3 elements in the formula, Oxyacid. Example Naming Oxyacids, H 2 SO 3, Continued 4. Identify the anion. SO 3 = SO 3 2- = sulfite 5. If the anion has ate suffix, change it to ic. If the anion has ite suffix, change it to ous. SO 3 2- = sulfite sulfurous 6. Write the name of the anion followed by the word acid. sulfurous acid 31

1. H 2 S Practice Name the Following 2. HClO 3 3. HNO 2 Practice Name the Following Continued 1. H 2 S hydrosulfuric acid. 2. HClO 3 chloric acid. 3. HNO 2 nitrous acid. 32

Writing Formulas for Acids When name ends in acid, formulas starts with H. Write formulas as if ionic, even though it is molecular. Hydro- prefix means it is binary acid, no prefix means it is an oxyacid. For an oxyacid, if ending is ic, polyatomic ion ends in ate; if ending is ous, polyatomic ion ends in ous. Example Binary Acids, Hydrosulfuric Acid 1. Write the symbol for the cation and its charge. 2. Write the symbol for the anion and its charge. 3. Charge (without sign) becomes subscript for the other ion. 4. Add (aq) to indicate dissolved in water. 5. Check that the total charge of the cations cancels the total charge of the anions. H + S 2- H + S 2- H 2 S (aq) In all acids, the cation is H +. Hydro- means binary. H 2 S H = (2) (+1) = +2 S = (1) (-2) = -2 33

Example Oxyacids, Carbonic Acid 1. Write the symbol for the cation and its charge. 2. Write the symbol for the anion and its charge. 3. Charge (without sign) becomes subscript for the other ion. 4. Add (aq) to indicate dissolved in water. 5. Check that the total charge of the cations cancels the total charge of the anions. H + CO 3 2- H + CO 3 2- H 2 CO 3 H 2 CO 3 (aq) In all acids, the cation is H +. No hydro- means polyatomic ion. -ic means -ate ion. H = (2) (+1) = +2 CO 3 = (1) (-2) = -2 Example Oxyacids, Sulfurous Acid 1. Write the symbol for the cation and its charge. 2. Write the symbol for the anion and its charge. 3. Charge (without sign) becomes subscript for the other ion. 4. Add (aq) to indicate dissolved in water. 5. Check that the total charge of the cations cancels the total charge of the anions. H + SO 3 2- H + SO 3 2- H 2 SO 3 H 2 SO 3 (aq) In all acids, the cation is H +. No hydro- means polyatomic ion. -ous means -ite ion. H = (2) (+1) = +2 SO 3 = (1) (-2) = -2 34

Practice What Are the Formulas for the Following Acids? 1. Chlorous acid 2. Phosphoric acid 3. Hydrobromic acid Practice What Are the Formulas for the Following Acids?, Continued 1. H + with ClO 2 HClO 2 2. H + with PO 4 3 H 3 PO 4 3. H + with Br HBr 35

Introductory Chemistry, 3 rd Edition Nivaldo Tro Chapter 5 Molecules and Compounds Based on notes of Roy Kennedy Massachusetts Bay Community College 2006, Prentice Hall Formula-to-Name Flowchart 36

5.11 What is the formula of the compound formed between lithium and nitrogen? 1. LiN 2 2. Li 2 N 3 3. Li 3 N 2 4. Li 3 N 5. LiN 5.11 What is the formula of the compound formed between lithium and nitrogen? 1. LiN 2 2. Li 2 N 3 3. Li 3 N 2 4. Li 3 N 5. LiN 37

5.17 The name of the compound NH 4 ClO 4 is: 1. Ammonium chloride 2. Ammonium chlorite 3. Ammonium hypochlorite 4. Ammonium chlorate 5. Ammonium perchlorate 5.17 The name of the compound NH 4 ClO 4 is: 1. Ammonium chloride 2. Ammonium chlorite 3. Ammonium hypochlorite 4. Ammonium chlorate 5. Ammonium perchlorate 38

5.19 The name of the compound PI 3 is: 1. Phosphorus iodide 2. Monophosphorus triiodide 3. Phosphorus triiodide 4. Phosphorus(III) iodide 5. Potassium iodide 5.19 The name of the compound PI 3 is: 1. Phosphorus iodide 2. Monophosphorus triiodide 3. Phosphorus triiodide 4. Phosphorus(III) iodide 5. Potassium iodide 39

5.20 The name of the compound HCN(aq) is: 1. Hydrocyanic acid 2. Hydrogen cyanide 3. Percyanic acid 4. Cyanic acid 5. Hypocyanous acid 5.20 The name of the compound HCN(aq) is: 1. Hydrocyanic acid 2. Hydrogen cyanide 3. Percyanic acid 4. Cyanic acid 5. Hypocyanous acid 40

5.24 The correct formula for ammonium dichromate is: 1. NH 4 Cr 2 2. NH 4 Cr 2 O 4 3. (NH 4 ) 2 Cr 2 O 4 4. NH 4 Cr 2 O 7 5. (NH 4 ) 2 Cr 2 O 7 5.24 The correct formula for ammonium dichromate is: 1. NH 4 Cr 2 2. NH 4 Cr 2 O 4 3. (NH 4 ) 2 Cr 2 O 4 4. NH 4 Cr 2 O 7 5. (NH 4 ) 2 Cr 2 O 7 41

5.25 The correct formula for dinitrogen tetrahydride is: 1. N 2 H 3 2. N 2 H 4 3. N 2 H 5 4. Ni 2 H 4 5. N 2 OH 4 5.25 The correct formula for dinitrogen tetrahydride is: 1. N 2 H 3 2. N 2 H 4 3. N 2 H 5 4. Ni 2 H 4 5. N 2 OH 4 42

5.26 Which of the following is named correctly? 1. HF (aq), hypofluorous acid 2. Na 2 HCO 3, sodium bicarbonate 3. PbO 2, lead oxide 4. SF 6, sulfur heptafluoride 5. NO 2 (aq), nitrous acid 5.26 Which of the following is named correctly? 1. HF (aq), hypofluorous acid 2. Na 2 HCO 3, sodium bicarbonate 3. PbO 2, lead oxide 4. SF 6, sulfur heptafluoride 5. HNO 2 (aq), nitrous acid 43

5.27 Which of the following is named incorrectly? 1. H 2 SO 4 (aq), sulfuric acid 2. SiO 2, silicon dioxide 3. CuCl 2, copper(ii) chloride 4. Zn(OH) 2, zinc(ii) hydroxide 5. NaClO, sodium hypochlorite 5.27 Which of the following is named incorrectly? 1. H 2 SO 4 (aq), sulfuric acid 2. SiO 2, silicon dioxide 3. CuCl 2, copper(ii) chloride 4. Zn(OH) 2, zinc(ii) hydroxide 5. NaClO, sodium hypochlorite 44

Formula Mass The mass of an individual molecule or formula unit. Also known as molecular mass or molecular weight. Sum of the masses of the atoms in a single molecule or formula unit. Whole = Sum of the parts. Mass of 1 molecule of H 2 O = 2(1.01 amu H) + 16.00 amu O = 18.02 amu. Practice Calculate the Formula Mass of Al 2 (SO 4 ) 3. 45

Practice Calculate the Formula Mass of Al 2 (SO 4 ) 3, Continued. Al = S = O = Al2 (SO4) 3 = 2 3 12 26.98 amu 32.07 amu 16.00 amu 342.17 amu 5.28 What is the formula mass of sodium sulfite? 1. 215.1 amu 2. 119.1 amu 3. 126.05 amu 4. 142.1 amu 5. 125.1 amu 46

5.28 What is the formula mass of sodium sulfite? 1. 215.1 amu 2. 119.1 amu 3. 126.05 amu 4. 142.1 amu 5. 125.1 amu 47