Solution Manual for Fundamentals of Logic Design 7th Edition by Roth pdf download
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Solution Manual for Fundamentals of Logic Design
7th Edition by Roth
Full download at: https://testbankbell.com/product/solution-manual-for-fundamentals-of-
logic-design-7th-edition-by-roth/
I: INTRODUCTION
The text, Fundamentals of Logic Design,7th edition, has been designed so that it
can be used either for a standard lecture course or for a self-paced course. The text is divided
into 20 study units in such a way that the average study time for each unit is about the same.
The units have undergone extensive class testing in a self-paced environment and have been
revised based on student feedback. The study guides and text material are sufficient to allow
almost all students to achieve mastery of all of the objectives. For example, the material on
Boolean algebra and algebraic simplification is 2½ units because students found this topic
difficult. There is a separate unit on going from problem statements to state graphs because
this topic is difficult for many students.
The textbook contains answers for all of the problems that are assigned in the study
guides. This Instructor’s Manual contains complete solutions to these problems. Solutions
to the remaining homework problems as well as all design and simulation exercises are also
included in this manual. In the solutions section of this manual, the abbreviation FLD stands
for Fundamentals of Logic Design (7th ed.).
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hardware description language. These units may be omitted if desired since no other units depend
on them.
Sequential circuits are given proper emphasis, with over half of the text devoted to this
subject. The pedagogical strategy the text uses in teaching sequential circuits has proven to be very
effective. The concepts of state, next state, etc. are first introduced for individual flip-flops, next
for counters, then for sequential circuits with inputs, and finally for more abstract sequential circuit
models. The use of timing charts, a subject neglected by many texts, is taught both because it is
a practical tool widely used by logic design engineers and because it aids in the understanding of
sequential circuit behavior.
The most important and often most difficult part of sequential circuit design is formulating
the state table or graph from the problem statement, but most texts devote only a few paragraphs
to this subject because there is no algorithm. This text devotes a full unit to the subject, presents
guidelines for deriving state tables and graphs, and provides programmed exercises that help the
student learn this material. Most of the material in the text is treated in a fairly conventional manner
with the following exceptions:
(1) The diagonal form of the 5-variable Karnaugh map is introduced in Unit 5. (We find
that students make fewer mistakes when using the diagonal form of 5-variable map in
comparison with the side-by-side form.) Unit 5 also presents a simple algorithm for finding
all essential prime implicants from a Karnaugh map.
(2) Both the state graph approach (Unit 18) and the SM chart approach (Unit 19) for designing
sequential control circuits are presented.
(3) The introduction to the VHDL hardware description language in Units 10, 17, and 20
emphasizes the relation between the VHDL code and the actual hardware.
The PSI method of instruction and its implementation are described in detail in the following
references:
1. Keller, Fred S. and J. Gilmour Sherman, The Keller Plan Handbook, W. A. Benjamin, Inc.,
1974.
2. Sherman, J.G., ed., Personalized System of Instruction: 41 Germinal Papers, W. A.
Benjamin, Inc., 1974.
3. Roth, C. H., The Personalized System of Instruction – 1962 to 1998, presented at the 1999
ASEE Annual Conference. (Go to http://search.asee.org and search under Conference
Papers for “The Personalized System of Instruction”.)
Results of applying PSI to a first course in logic design of digital systems are described in
Roth, C.H., Continuing Effectiveness of Personalized Self-Paced Instruction in Digital Systems
Engineering, Engineering Education, Vol. 63, No. 6, March 1973.
The instructor in charge of a self-paced course will serve as course manager in addition to
his role in the classroom. For a small class, he may spend a good part of his time acting as proctor
in the classroom, but as class size increases he will have to devote more of his time to supervision
of course activities and less time to individual interaction with students. In his managerial role, the
instructor is responsible for organizing the course, selection and training of proctors, supervision
of proctors, and monitoring of student progress. The proctors play an important role in the success
of a self-paced course, and therefore their selection, training, and supervision is very important.
After an initial session to discuss proper ways of grading readiness tests and interacting with
students, weekly proctor meetings to discuss course procedures and problems may be appropriate.
A progress chart showing the units completed by each student is very helpful in
monitoring student progress through the course. The instructor may wish to have individual
conferences with students who fall too far behind. The instructor needs to be available in the
classroom to answer individual student questions and to assist with grading of readiness tests
as needed. He should make a special point to speak with the weak or slow students and give
them a word of encouragement. From time to time he may need to settle differences which arise
between proctors and students.
Various strategies for organizing a PSI course are described in the Keller Plan
Handbook. The procedures previously used for operating the self-paced digital logic course
at the University of Texas are described in “Unit 0”, which is available from Prof. Charles H.
Roth, [email protected]. At the first class meeting, we handed out a copy of Unit 0. The
students were asked to read through Unit 0 and take a short test on the course procedures.
This test was immediately evaluated so that the student could complete Unit 0 before the
end of the first class period. In this way, the student was exposed to the basic way the course
operated and was ready to proceed immediately with Unit 1 in the textbook.
During a typical class period, some of the students spent their time studying but most
of the students came prepared to take a unit test. At the beginning of the period, the instructor
or a proctor was available to answer student questions on an individual basis. Later in the
4
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period, most of the time was spent evaluating unit tests. We found that a standard 50 minute
class period was not long enough for a PSI session. We usually scheduled sessions of 1½ or
2 hours or longer depending on class size. This allowed adequate time for students to have
their questions answered, take a unit test, and have their tests graded. Interactive grading of
the tests with the student present is an important part of the PSI system and adequate time must
be allowed for this activity. If you have a large number of students and proctors, you may
wish to prepare a manual for guidance of your proctors. The procedures that we used for
evaluating unit tests are described in a Proctor’s Manual, which can be obtained by writing
to Professor Charles H. Roth.
SimUaid provides an easy way for students to test their logic designs by simulating them.
We first introduce SimUaid in Unit 4, where we ask the students to design a simple logic circuit such
as problem 4.13 or 4.14, and simulate it. SimUaid is easy to learn, and it is highly interactive so that
students can flip a simulated switch and immediately observe the result. In Unit 8, students design a
multiple-output combinational logic circuit using NAND and NOR gates and test its operation using
SimUaid. Students can use the simulator to help them understand the operation of latches and flip-flops
in Unit 11. In Unit 12, we ask them to design a counter and simulate it (one part of problem 12.10). In
Unit 16, students use SimUaid to test their sequential circuit designs. They can also generate VHDL
code from their SimUaid circuit, synthesize it, and download it to a circuit board for hardware testing.
In Unit 18, students can use the advanced features of SimUaid to simulate a multiplier or divider
controlled by a state machine.
LogicAid provides an easy way to introduce students to the use of the computer in the logic
design process. It enables them to solve larger, more practical design problems than they could by
hand. They can also use LogicAid to verify solutions that they have worked out by hand. Instructors
can use the program for grading homework and quizzes. We first introduce LogicAid in Unit 5. The
program has a Karnaugh Map Tutorial mode that is very useful in teaching students to solve Karnaugh
map problems. This tutorial mode helps students learn to derive minimum solutions from a Karnaugh
map by informing them at each step whether that step is correct or not. It also forces them to choose
essential prime implicants first. When in the KMap tutor mode, LogicAid prints “KMT” at the top of
each output page, so you can check to see if the problems were actually solved in the tutorial mode.
Students can use LogicAid to help them solve design problems in Units 8, 16, 18, 19 and other
units. For designing sequential circuits, they can input a state graph, convert it to a state table, reduce
the state table, make a state assignment, and derive minimized logic equations for outputs and flip-flop
inputs.
The LogicAid State Table Checker is useful for Units 14 and 16, and for other units in which
students construct state tables. It allows students to check their solutions without revealing the correct
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answers. If the solution is wrong, the program displays a short input sequence for which the student’s
table fails. The LogicAid folder on the CD contains encoded copies of solutions for most of the state
graph problems in Fundamentals of Logic Design, 7th Ed. If you wish to create a password-protected
solution file for other state table problems, enter the state table into LogicAid, syntax check it, and
then hold down the Ctrl key while you select Save As on the file menu. The Partial Graph Checker
serves as a state graph tutor that allows a student to check his work at each step while constructing
a state graph. If the student makes a mistake, it provides feedback so that the student can correct his
answer. The partial graph checker works with any state graph problem for which an encoded state table
solution file is provided.
The DirectVHDL simulator helps students learn VHDL syntax because it provides immediate
visual feedback when they make mistakes. Our students use it for simulating VHDL code in Units 10,
17, and 20. Students can simulate and debug their code at home and then bring the code into lab for
synthesis and hardware testing.
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Unit 1 Solutions
II. SOLUTIONS TO HOMEWORK PROBLEMS
Unit 1 Problem Solutions
1.1 (a) 757.2510 1.1 (b) 123.1710
16 | 757 0.25 16 | 123 0.17
16 | 47 r5 16 16 | 7 r11 16
16 | 2 r15=F16 (4).00 0 r7 (2).72
0 r2 16
(11).52
∴ 757.2510 = 2F5.4016 16
= 0010 1111 0101.0100 00002 (8).32
2 F 5 4 0
1.1 (c) 356.89 ∴123.1710 = 7B.2B16
2
10
16 | 356 0.89 = 0111 1011.0010 1011
7 B 2 B
16 | 22 r4 16
16 | 1 r6 (14).24 1.1 (d) 1063.510
0 r1 16 16 | 1063 0.5
(3).84 16 | 66 r7 16
16 16 | 4 r2 (8).00
(13).44 0 r4
16
(7).04 ∴1063.510 = 427.816
= 0100 0010 0111.10002
∴ 356.8910 = 164.E316 4 2 7 8
7
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Unit 1 Solutions
464
6 5B1.1C16 = 010110110001.00011100 2=2661.070 8
(1).4784 2 6 6 1 0 7 0
8
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Unit 1 Solutions
1.5 (a) 1 11
1111 (Multiply) 1.5 (b, c) See FLD p. 730 for solutions.
1111 (Add) ×1010
+1010 0000
11001 1111 1.6, 1.7, See FLD p. 730 for solutions.
11110 1.8, 1.9
1111 (Sub) 0000
1.10 (a) 1305.37510
−1010 011110
0101 1111 16 | 1305 0.375
10010110 16 | 81 r9 16
5 r1 (6).000
6 r15 = F16 16 5 1 9 6 0 0
(5).28 1.10 (c) 301.1210
16 16 | 301 0.12
(4).48 16 | 18 r13 16
1 r2 (1).92
∴ 111.3310 = 6F.5416 16
9
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Unit 1 Solutions
4|1 r2 (3).84 9 | 15 r5 (8).46
0 r1 4 9|1 r6 9
(3).36 0 r1 (4).14
∴ 384.7410 = 12000.2331134...
∴ A52.A411 = 1267.9410 = 1657.84279...
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Unit 1 Solutions
1.13 544.1 = 5 × 92 + 4 × 91 + 4 × 90 + 1 × 9–1 1.14 (a), (c) 16 | 97 .7
9
= 5 × 81 + 4 × 9 + 4 + 1/9 (b), (c) 16 | 6 r1 16
= 445 1/910 0 r6 (11).2
16 | 445 1/9 16
16 | 27 r13 16 (3).2
16 | 1 r11 (1)7/9 ∴ 97.710 = 61.B3333....16
0 r1 16 (a) 61.B3333..16
(12)4/9 = 110 0001.1011 0011 0011 0011 0011... 2
16 (b) 1 100 001.101 100 110 011 001 100 11... 2
(7)1/9 = 141.5 4631 4631.... 8
∴ 544.19 = 1BD.1C716
= 1 1011 1101.0001 1100 01112...
∴ 2983 63/6410 = 5647.768 (or 5647.778) ∴ 93.7010 = 135.548 = 001 011 101.101 1002
= 101 110 100 111.111 1102
(or 101 110 100 111.111 1112)
11
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Unit 1 Solutions
1.17 (a) 111 111 1.17 (b) 1 11 11
1111 (Add) 1111 (Subtract) 1101001(Add) 1101001 (Sub)
1001 1001 110110 110110
11000 0110 10011111 110011
13
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Unit 1 Solutions
1.20(b) 100011 Quotient 1.20(c) 1011 Quotient
1011 )110000011 1010 )1110100
1011 1010
10001 10010
1011 1010
1101 10000
1011 1010
10 Remainder 110 Remainder
1.21 (a) 4 + 3 is 10 in base 7, i.e., the sum digit is 1.22 If the binary number has n bits (to the right of the
0 with a carry of 1 to the next column. 1 + 5 + radix point), then its precision is (1/2n+1). So to
4 is 10 in base 7. 1 + 6 + 0 is 10 in base 7. This have the same precision, n must satisfy
overflows since the correct sum is 10007.
(b) 4 + 3 + 3 + 3 = 13 in base 10 and 23 in base (1/2n+1) < (1/2)(1/104) or n > 4/(log 2) = 13.28 so n
5. Try base 10. 1 + 2 + 4 + 1 + 3 = 11 in base 10 so must be 14.
base 10 does not produce a sum digit of 2. Try base
5. 2 + 2 + 4 + 1 + 3 = 22 in base 5 so base 5 works.
1.23
(c) 4 + 3 + 3 + 3 = 31 in base 4, 21 in base 6,
.363636....
and 11 in base 12. Try base 12. 1 + 2 + 4 + 1 + 3 =
= (36/102)(1 + 1/102 + 1/104 + 1/106 + …)
B in base 12 so base 12 does not work. Try base 4.
= (36/102)[1/(1 – 1/102)] = (36/102)[102/99]
3 + 2 + 4 + 1 + 3 = 31 in base 4 so base 4 does not
= 36/99 = 4/11
work. Try base 6. 2 + 2 + 4 + 1 + 3 = 20 so base 6
8(4/11) = 2 + 10/11
is correct.
8(10/11) = 7 + 3/11
8(3/11) = 2 + 2/11
8(2/11) = 1 + 5/11
1.24 (a) Expand the base b number into a power series
8(5/11) =3 + 7/11
N = d3k-1b3k-1 + d3k-2b3k-2 + d3k-3b3k-3 + …. + d5b5
8(7/11) = 5+ 1/11
+ d4b4 + d3b3 + d2b2 + d1b1 + d0b0 + d-1b-1 + d b- 8(1/11) = 0 + 8/11
-2
2 + d-3b-3 + …. + d-3m+2b-3m+2 + d-3m+1b-3m+1 8(8/11) = 5 + 9/11
+ d-3mb-3m where each di has a value from 0 to 8(9/11) = 6 + 6/11
(b-1). (Note that 0’s can be appended to the number 8(6/11) = 4 + 4/11
so that it has a multiple of 3 digits to the left and 8(4/11) = 2 + 10/11
right of the radix point.) Factor b3 from each group Repeats: .27213505642…….
of 3 consecutive digits of the number to obtain
N = (d3k-1b2 + d3k-2b1 + d3k-3b0)(b3)(k-1) + ….
1.24 (b) Expand the base b3 number into a power series
+ (d5b2 + d4b1 + d3b0)(b3)1 + (d2b2 + d1b1 +
N = dk(b3)k + dk-1(b3)k-1 + … + d1(b3)1 + d0(b3)0
d0b0 )(b3)0 + (d-1b2 + d-2b1 + d-3b0)(b3)-1 + …. +
+ d-1(b3)-1 + …. + d-m(b3)-m
(d-3m+2b2 + d-3m+1b1 + d-3mb0)(b3)-m where each di has a value from 0 to (b3 -1).
Each (d3i-1b2 + d3i-2b1 + d3i-3b0) has a value from Consequently, di can be represented as a base b
0 to [(b-1)b2 + (b-1)b1 + (b-1)b0] number in the form
= (b-1)( b2 + b1 + b0) = (b3-1) (e3i-1b2 + e3i-2b1 + e3i-3b0) Where each e
j
so it is a valid digit in a base b3 number. has a value from 0 to (b-1). Substituting these
Consequently, the last expression is the power expressions for the di produces a power series
series expansion for a base b3 number. expansion for a base b number.
1.25(a) (5 - 1) = 45, (52 - 1) = 445 and (53 - 1) = 4445 1.26(a) (b + 1)2 = b2 + 2b + 1 so (11b)2 = 121b if b > 2.
15
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Unit 1 Solutions
1.27(a) (0.12)3 = (1/3 + 2/9)10 = (2/6 + 8/36)10 1.28 1.29
= (3/6 + 2/36)10 = (0.32)6 5-3-1-1 is possible, but
43 2 1
1.27(b) (0.375)10 = (3/8)10 = (0.3)8 6-4-1-1 is not, because
0 00 0 0 there is no way to
1.27(c) (a-1R-1 + a-2R-2 + ... + a-mR-m)Sn will be an 1 00 0 1 represent 3 or 9.
integer for every N only if Rm divides Sn for 2 00 1 0 Alternate
some n. Hence, each factor of R must be a factor Solutions:
of S, not necessarily the same number of times. 3 01 0 0
1.27(d) 4 10 0 0 5311
For a specific number N, (a-1R-1 + a-2R-2 + ...
+ a-mR-m)Sn will be an integer if each factor of 5 10 0 1 0 0000
Rm is a factor of either Sn or 6 10 1 0 1 0001 (0010)
(a-1Rm-1 + a-2Rm-2 + ... + a-m) 2 0011
7 11 0 0
1.30 5-4-1-1 is not possible, because there is no way to 3 0100
8 11 0 1
represent 3 or 8. 6-3-2-1 is possible: 4 0101
9 11 1 0 (0110)
6321 5 1000
9154 = 6 1001 (1010)
0 0000 1110 0001 1001 1000 7 1011
1 0001
8 1100
2 0010
9 1101 (1110)
3 0100
4 0101 1.32
5 0110 1.31 Alternate Alternate
6 1000 Solutions: Solutions:
7 1001 62 21 5221
8 1010 0 00 00 0 0000
9 1100 1 00 01 1 0001
2 00 10 (0100) (0100)
1.33 Alternate 2 0010
3 00 11 (0101) (0101)
Solutions: 3 0011
4 01 10 4 0110
73 21 5 01 11 5 1000
0 00 00 6 10 00 6 1001
1 00 01 7 10 01 7 1010 (1100)
8 10 10 (1100) (1101)
2 00 10 8 1011
9 10 11 (1101)
3 01 00 (0011) 9 1110
4 01 01 1100 0011 = 83 1110 0110 = 94
5 01 10
6 01 11 (a) 8 4 -2-1 (b)
1.34
7 10 00 The 9’s
0 00 00
8 10 01 complement
1 01 11 of a decimal
9 10 10
2 01 10 number
A 11 00 represented
3 01 01
B 11 01 (1011) with this
4 01 00
weighted code
5 10 11
can be obtained
B4A9 = 1101 0101 1100 1010 6 10 10 by replacing
Alt.: = " " 1011 " 7 10 01 0's with 1's
8 10 00 and 1's with
0's (bit-by-bit
9 11 11
16
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Unit 1 Solutions
complement).
17
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Unit 1 Solutions
1.35 (a) 222.2210 1.35 (b) 183.8110
16 | 222 0.22 16 | 183 0.81
16 | 13 r14 16 16 | 11 r7 16
0 r13 (3).52 0 r11 (12).96
16 16
(8).32 (15).36
1.36 (a) In 2’s complement In 1’s complement 1.36 (b) In 2’s complement In 1’s complement
(–10) + (–11) (–10) + (–11) (–10) + (–6) (–10) + (–6)
110110 110101 110110 110101
110101 110100 111010 111001
(1)101011 (–21) (1)101001 (1)110000 (–16) (1)101110
1 1
101010 (–21) 101111 (–16)
1.36 (c) In 2’s complement In 1’s complement 1.36(d) In 2’s complement In 1’s complement
(–8) + (–11) (–8) + (–11) 11 + 9 11 + 9
111000 110111 001011 001011
110101 110100 001001 001001
(1)101101 (–19) (1)101011 010100 (20) 010100 (20)
1
101100 (–19)
1.36 (e) In 2’s complement In 1’s complement 1.37 (a) 01001-11010
(–11) + (–4) (–11) + (–4) In 2’s complement In 1’s complement
110101 110100 01001 01001
111100 111011 + 00110 + 00101
(1)110001 (–15) ( )101111 01111 01110
1 1
110000 (–15)
1.37 (b) In 2’s complement In 1’s complement 1.37 (c) In 2’s complement In 1’s complement
11010 11010 10110 10110
+ 00111 + 00110 + 10011 + 10010
(1)00001 (1)00000 (1)01001 (1)01000
1 overflow 1
00001 01001
overflow
1.37 (d) In 2’s complement In 1’s complement 1.37 (e) In 2’s complement In 1’s complement
11011 11011 11100 11100
+ 11001 + 11000 + 01011 + 01010
(1)10100 (1)10011 (1)00111 (1)00110
1 1
10100 00111
1.38 (a) In 2’s complement In 1’s complement 1.38 (b) In 2’s complement In 1’s complement
11010 11010 01011 01011
+ 01100 + 01011 + 01000 + 00111
(1)00110 (1)00101 10011 10010
1
00110
18
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Unit 1 Solutions
1.38 (c) In 2’s complement In 1’s complement 1.38 (d) In 2’s complement In 1’s complement
10001 10001 10101 10101
+ 10110 + 10101 + 00110 + 00101
(1)00111 (1)00110 11011 11010
overflow 1
00111
overflow
1.39 (a) add subt 1.40 (a) complement
101010 101010 i) 00000000 (0) 11111111 (-0)
+ 011101 - 011101 ii) 11111110 (-1) 00000001 (1)
(1)000111 001101 iii) 00110011 (51) 11001100 (-51)
1 overflow iv) 10000000 (-127) 01111111 (127)
001000
(b)
(b) add subt i) 00000000 (0) 00000000 (0)
101010 101010 ii) 11111110 (-2) 00000010 (2)
+ 011101 - 011101 iii) 00110011 (51) 11001101 (-51)
(1)000111 001101 iv) 10000000 (-128) 10000000 (-128)
overflow
1.41 (a) (16)(4) = 64, add 2 0’s to get 6400 1.42 (a) If A + B < 2n-1 - 1, then the sign bit of A + B is
(10)(2) = 20, add 1 0 to get 200 0 indicating a positive number with magnitude
(7)(1) = 7 A + B. If A + B > 2n-1 - 1, then the sign bit
6400 + 200 + 7 = 6607 of A + B is 1 indicating a negative number with
n
magnitude 2 - (A + B).
(b) (dn-1dn-2 … d1d0)20 = dn-1(20)n-1 +
1.43 A and B positive: Overflow does not occur if result represents a negative number with magnitude (B - A).
A + B < 2n - 1 - 1 in which case A + B has a sign
bit of 0 and has a magnitude of A + B.
A positive and B negative and A > |B|: A + 2n -
1 - B = 2n - 1 + (A - B) > 2n - 1 so there is a carry
from the sign position and, after the end-around
carry, the result is (A - B).
A positive and B negative and A < |B|: A + 2n -
1 - B = 2n - 1 - (B - A) < 2n - 1 so there is no carry
from the sign position and the sign bit is 1 so the
19
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Unit 1 Solutions
1.43 if A + B < 2n - 1 - 1 in which case
cont. 2n - 1 - (A + B) > 2n - 1 so the sign bit is
A and B 1 and the result represents a negative
negative: number with magnitude (A + B).
(2n - 1 - A)
+ (2n - 1 -
B) =
2
n
-
1
-
(
A
+
B
)
a
f
t
e
r
t
h
e
e
n
d
-
a
r
o
u
n
d
c
a
r
r
y
.
T
h
e
r
e
i
s
n
o
o
v
e
r
f
l
o
w 20
© 2014 Cengage Learning. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
Unit 1 Solutions
1.44 Two positive numbers 1.45 There is no overflow if the carry into the sign
No overflow: 0x…x + 0x…x = 0x…x position equals the carry out of the sign position.
carry in = 0 = carry out There is overflow if the carry into the sign position
Overflow: 0x…x + 0x…x = 1x…x does not equal the carry out of the sign position
carry in = 1, carry out = 0 unless an end around carry causes a carry into the
sign position.
Two negative numbers
No overflow: 1x…x + 1x…x = 1x…x No overflow Overflow
21
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Unit 1 Solutions
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chloride even on prolonged heating (Liés-Bodart), but an alloy of sodium
with zinc, lead, and bismuth decomposes it, forming an alloy of calcium
with one of the above-named metals (Caron). The zinc alloy may be
obtained with as much as 15 p.c. of calcium. Calcium chloride is soluble
in alcohol and absorbs ammonia.
A gram molecular weight of calcium chloride in dissolving in an excess
of water evolves 18,723 calories, and in dissolving in alcohol 17,555 units
of heat, according to Pickering.
Roozeboom made detailed researches on the crystallo-hydrates of
calcium chloride (1889), and found that CaCl2,6H2O melts at 30·2°, and
is formed at low temperatures from solutions containing not more than
103 parts of calcium chloride per 100 parts of water; if the amount of salt
(always to 100 parts of water) reaches 120 parts, then tabular crystals of
CaCl2,4H2Oβ are formed, which at temperatures above 38·4° are
converted into the crystallo-hydrates CaCl2,2H2O, whilst at temperatures
below 18° the β variety passes into the more stable CaCl2,4H2Oα, which
process is aided by mechanical friction. Hence, as is the case with
magnesium sulphate (Note 27), one and the same crystallo-hydrate
appears in two forms—the β, which is easily produced but is unstable,
and the α, which is stable. The solubility of the above-mentioned
hydrates of chloride of calcium, or amount of calcium chloride per 100
parts of water, is as follows:—
0° 20° 30° 40° 60°
CaCl2,6H2O 60 75 100 (102·8)
CaCl2,4H2Oα — 90 101 117
(154·2)
CaCl2,4H2Oβ — 104 114 —
CaCl2,2H2O — — (308·3) 128 137
The amount of calcium chloride to 100 parts of water in the crystallo-
hydrate is given in brackets. The point of intersection of the curves of
solubility lies at about 30° for the first two salts and about 45° for the
salts with 4H2O and 2H2O. The crystals CaCl2,2H2O may, however, be
obtained (Ditte) at the ordinary temperature from solutions containing
hydrochloric acid. The vapour tension of this crystallo-hydrate equals the
atmospheric at 165°, and therefore the crystals may be dried in an
atmosphere of steam and obtained without a mother liquor, whose
vapour tension is greater. This crystallo-hydrate decomposes at about
175° into CaCl2,H2O and a solution; this is easily brought about in a
closed vessel when the pressure is greater than the atmosphere. This
crystallo-hydrate is destroyed at temperatures above 260°, anhydrous
calcium chloride being formed.
Neglecting the unstable modification CaCl2,4H2Oβ, we will give the
temperatures t at which the passage of one hydrate into another takes
place and at which the solution CaCl2 + nH2O, the two solids A and B and
aqueous vapour, whose tension is given as p in millimetres, are able to
exist together in stable equilibrium, according to Roozeboom's
determinations:
t n A B p
-55° 14·5 ice CaCl2,6H2O 0
+29·8° 6·1 CaCl2,6H2O CaCl2,4H2O 6·8
45·3° 4·7 CaCl2,4H2O CaCl2,2H2O 11·8
175·5° 2·1 CaCl2,2H2O CaCl2,H2O 842
200° 1·8 CaCl2,H2O CaCl2 Several atmospheres
Solutions of calcium chloride may serve as a convenient example for
the study of the supersaturated state, which in this case easily occurs,
because different hydrates are formed. Thus at 25° solutions containing
more than 83 parts of anhydrous calcium chloride per 100 of water will
be supersaturated for the hydrate CaCl2,6H2O.
On the other hand, Hammerl showed that solutions of calcium chloride,
when frozen, deposit ice if they contain less than 43 parts of salt per 100
of water, and if more the crystallo-hydrate CaCl2,6H2O separates, and
that a solution of the above composition (CaCl2,14H2O requires 44·0
parts calcium chloride per 100 of water) solidifies as a cryohydrate at
about -55°.
[51] The action of barium sulphate on sodium and potassium
carbonates is given on p. 437.
[52] Barium sulphide is decomposed by water, BaS + 2H2O = H2S +
Ba(OH)2 (the reaction is reversible), but both substances are soluble in
water, and their separation is complicated by the fact that barium
sulphide absorbs oxygen and gives insoluble barium sulphate. The
hydrogen sulphide is sometimes removed from the solution by boiling
with the oxides of copper or zinc. If sugar be added to a solution of
barium sulphide, barium saccharate is precipitated on heating; it is
decomposed by carbonic anhydride, so that barium carbonate is formed.
An equivalent mixture of sodium sulphate with barium or strontium
sulphates when ignited with charcoal gives a mixture of sodium sulphide
and barium or strontium sulphide, and if this mixture be dissolved in
water and the solution evaporated, barium or strontium hydroxide
crystallises out on cooling, and sodium hydrosulphide, NaHS, is obtained
in solution. The hydroxides BaH2O2 and SrH2O2 are prepared on a large
scale, being applied to many reactions; for example, strontium hydroxide
is prepared for sugar works for extracting crystallisable sugar from
molasses.
We may remark that Boussingault, by igniting barium sulphate in
hydrochloric acid gas, obtained a complete decomposition, with the
formation of barium chloride. Attention should also be turned to the fact
that Grouven, by beating a mixture of charcoal and strontium sulphate
with magnesium and potassium sulphates, showed the easy
decomposability depending on the formation of double salts, such as
SrS,K2S, which are easily soluble in water, and give a precipitate of
strontium carbonate with carbonic anhydride. In such examples as these
we see that the force which binds double salts may play a part in
directing the course of reactions, and the number of double salts of silica
on the earth's surface shows that nature takes advantage of these forces
in her chemical processes. It is worthy of remark that Buchner (1893), by
mixing a 40 per cent. solution of barium acetate with a 60 per cent.
solution of sulphate of alumina, obtained a thick glutinous mass, which
only gave a precipitate of BaSO4 after being diluted with water.
[53] Barium sulphate is sometimes converted into barium chloride in
the following manner: finely-ground barium sulphate is heated with coal
and manganese chloride (the residue from the manufacture of chlorine).
The mass becomes semi-liquid, and when it evolves carbonic oxide the
heating is stopped. The following double decompositions proceed during
this operation: first the carbon takes up the oxygen from the barium
sulphate, and gives sulphide, BaS, which enters into double
decomposition with the chloride of manganese, MnCl2, forming
manganese sulphide, MnS, which is insoluble in water, and soluble barium
chloride. This solution is easily obtained pure because many foreign
impurities, such as iron, remain in the insoluble portion with the
manganese. The solution of barium chloride is chiefly used for the
preparation of barium sulphate, which is precipitated by sulphuric acid, by
which means barium sulphate is re-formed as a powder. This salt is
characterised by the fact that it is unacted on by the majority of chemical
reagents, is insoluble in water, and is not dissolved by acids. Owing to
this, artificial barium sulphate forms a permanent white paint which is
used instead of (and mixed with) white lead, and has been termed ‘blanc
fixé’ or ‘permanent white.’
The solution of one part of calcium chloride at 20° requires 1·36 part of
water, the solution of one part of strontium chloride requires 1·88 part of
water at the same temperature, and the solution of barium chloride 2·88
parts of water. The solubility of the bromides and iodides varies in the
same proportion. The chlorides of barium and strontium crystallise out
from solution with great ease in combination with water; they form
BaCl2,2H2O and SrCl2,6H2O. The latter (which separates out at 40°)
resembles the salts of Ca and Mg in composition, and Étard (1892)
obtained SrCl2,2H2O from solutions at 90–130°. We may also observe
that the crystallo-hydrates BaBr2,H2O and BaI2,7H2O are known.
[54] The nitrates Sr(NO3)2 (in the cold its solutions give a crystallo-
hydrate containing 4H2O) and Ba(NO3)2 are so very sparingly soluble in
water that they separate in considerable quantities when a solution of
sodium nitrate is added to a strong solution of either barium or strontium
chloride. They are obtained by the action of nitric acid on the carbonates
or oxides. 100 parts of water at 15° dissolve 6·5 parts of strontium
nitrate and 8·2 parts of barium nitrate, whilst more than 300 parts of
calcium nitrate are soluble at the same temperature. Strontium nitrate
communicates a crimson coloration to the flame of burning substances,
and is therefore frequently used for Bengal fire, fireworks, and signal
lights, for which purpose the salts of lithium are still better fitted. Calcium
nitrate is exceedingly hygroscopic. Barium nitrate, on the contrary, does
not show this property in the least degree, and in this respect it
resembles potassium nitrate, and is therefore used instead of the latter
for the preparation of a gunpowder which is called ‘saxifragin powder’ (76
parts of barium nitrate, 2 parts of nitre, and 22 parts of charcoal).
[55] The dissociation of the crystallo-hydrate of baryta is given in
Chapter I., Note 65. 100 parts of water dissolve
0° 20° 40° 60° 80°
BaO 1·5 3·5 7·4 18·8 90·8
SrO 0·3 0·7 1·4 3 9
Supersaturated solutions are easily formed.
The anhydrous oxide BaO fuses in the oxyhydrogen flame. When
ignited in the vapour of potassium, the latter takes up the oxygen; whilst
in chlorine, oxygen is separated and barium chloride formed.
[55 bis] Brugellmann, by heating BaH2O2 in a graphite or clay crucible,
obtained BaO in needles, sp. gr. 5·32, and by heating in a platinum
crucible—in crystals belonging to the cubical system, sp. gr. 5·74. SrO is
obtained in the latter form from the nitrate. The following are the specific
gravities of the oxides from different sources:—
MgO CaO SrO
from RN2O6 3·38 3·25 4·75
„ RCO3 3·48 3·26 4·45
„ RH2O2 3·41 3·25 4·57
[56] The property of barium oxide of absorbing oxygen when heated,
and giving the peroxide, BaO2, is very characteristic for this oxide (see
Chapter III., Note 7). It only belongs to the anhydrous oxide. The
hydroxide does not absorb oxygen. Peroxides of calcium and strontium
may be obtained by means of hydrogen peroxide. Barium peroxide is
insoluble in water, but is able to form a hydrate with it, and also to
combine with hydrogen peroxide, forming a very unstable compound
having the composition BaH2O4 (obtained by Professor Schöne), which in
course of time evolves oxygen (Chapter IV., Note 21).
[57] Even in solutions a gradual progression in the increase of the
specific gravity shows itself, not only for equivalent solutions (for
instance, RCl2 + 200H2O), but even with an equal percentage
composition, as is seen from the curves giving the specific gravity (water
4° = 10,000) at 15° (for barium chloride, according to Bourdiakoff's
determinations):
BeCl2: S = 9,992 + 67·21p + 0·111p2
CaCl2: S = 9,992 + 80·24p + 0·476p2
SrCl2: S = 9,992 + 85·57p + 0·733p2
BaCl2: S = 9,992 + 86·56p + 0·813p2
[58] One part of calcium sulphate at the ordinary temperature requires
about 500 parts of water for solution, strontium sulphate about 7,000
parts, barium sulphate about 400,000 parts, whilst beryllium sulphate is
easily soluble in water.
[59] We refer beryllium to the class of the bivalent metals of the
alkaline earths—that is, we ascribe to its oxide the formula BeO, and do
not consider it as trivalent (Be = 13·5, Chapter VII., Note 21), although
that view has been upheld by many chemists. The true atomic
composition of beryllium oxide was first given by the Russian chemist,
Avdéeff (1819), in his researches on the compounds of this metal. He
compared the compounds of beryllium to those of magnesium, and
refuted the notion prevalent at the time, of the resemblance between the
oxides of beryllium and aluminium, by proving that beryllium sulphate
presents a greater resemblance to magnesium sulphate than to
aluminium sulphate. It was especially noticed that the analogues of
alumina give alums, whilst beryllium oxide, although it is a feeble base,
easily giving, like magnesia, basic and double salts, does not form true
alums. The establishment of the periodic system of the elements (1869),
considered in the following chapter, immediately indicated that Avdéeff's
view corresponded with the truth—that is, that beryllium is bivalent,
which therefore necessitated the denial of its trivalency. This scientific
controversy resulted in a long series of researches (1870–80) concerning
this element, and ended in Nilson and Pettersson—two of the chief
advocates of the trivalency of beryllium—determining the vapour density
of BeCl2 = 40, (Chapter VII., Note 21), which gave an undoubted proof of
its bivalency (see also Note 3).
[60] Beryllium oxide, like aluminium oxide, is precipitated from
solutions of its salts by alkalis as a gelatinous hydroxide, BeH2O2, which,
like alumina, is soluble in an excess of caustic potash or soda. This
reaction may be taken advantage of for distinguishing and separating
beryllium from aluminium, because when the alkaline solution is diluted
with water and boiled, beryllium hydroxide is precipitated, whilst the
alumina remains in solution. The solubility of the beryllium oxide at once
clearly indicates its feeble basic properties, and, as it were, separates this
oxide from the class of the alkaline earths. But on arranging the oxides of
the above-described metals of the alkaline earths according to their
decreasing atomic weights we have the series
BaO, SrO, CaO, MgO, BeO,
in which the basic properties and solubility of the oxides consecutively
and distinctly decrease until we reach a point when, had we not known of
the existence of the beryllium oxide, we should expect to find in its place
an oxide insoluble in water and of feeble basic properties. If an alcoholic
solution of caustic potash be saturated with the hydrate of BeO, and
evaporated under the receiver of an air pump, it forms silky crystals
BeK2O2.
Another characteristic of the salts of beryllium is that they give with
aqueous ammonia a gelatinous precipitate which is soluble in an excess
of ammonium carbonate like the precipitate of magnesia; in this beryllium
oxide differs from the oxide of aluminium. Beryllium oxide easily forms a
carbonate which is insoluble in water, and resembles magnesium
carbonate in many respects. Beryllium sulphate is distinguished by its
considerable solubility in water—thus, at the ordinary temperature it
dissolves in an equal weight of water; it crystallises out from its solutions
in well-formed crystals, which do not change in the air, and contain
BeSO4,4H2O. When ignited it leaves beryllium oxide, but this oxide, after
prolonged ignition, is re-dissolved by sulphuric acid, whilst aluminium
sulphate, after a similar treatment, leaves aluminium oxide, which is no
longer soluble in acids. With a few exceptions, the salts of beryllium
crystallise with great difficulty, and to a considerable extent resemble the
salts of magnesium; thus, for instance, beryllium chloride is analogous to
magnesium chloride. It is volatile in an anhydrous state, and in a
hydrated state it decomposes, with the evolution of hydrochloric acid.
[61] Thus in the nitrides of the metals we have substances by means
of which we can easily obtain from the nitrogen of the air, not only
ammonia, but also with the aid of CO, by synthesis, a whole series of
complex carbon and nitrogen compounds.
[62] As the hydrides of calcium, magnesium, &c. are very stable under
the action of heat, and these metals and hydrogen occur in the sun, it is
likely that the formation of their hydrides may take place there. (Private
communication from Prof. Winkler, 1894.) It is probable that in the free
metals of the alkaline earths hitherto obtained a portion was frequently in
combination with nitrogen and hydrogen.
[63] Thus, for instance, a mixture of 56 parts of CaO and 24 parts of
magnesium powder is heated in an iron pipe (placed over a row of gas
burners as in the combustion furnace used for organic analysis) in a
stream of hydrogen. After being heated for ½ hour the mixture is found
to absorb hydrogen (it no longer passes over the mixture, but is retained
by it). The product, which is light grey, and slightly coherent, disengages
a mass of hydrogen when water is poured over it, and burns when
heated in air. The resultant mass contains 33 per cent. CaH, about 28 per
cent. CaO, and about 38 per cent. MgO. Neither CaH nor any other MH
has yet been obtained in a pure state.
The acetylene derivatives of the metals of the alkaline earths C2M
(Chapter VIII., Note 12 bis), for instance, C2Ba, obtained by Maquenne
and Moissan, belong to the same class of analogous compounds. It must
here be remarked that the oxides MO of the metals of the alkaline earths,
although not reducible by carbon at a furnace heat, yet under the action
of the heat attained in electrical furnaces, not only give up their oxygen
to carbon (probably partly owing to the action of the current), but also
combine with carbon. The resultant compounds, C2M, evolve acetylene,
C2H2, with HCl, just as N2M3 give ammonia. We may remark moreover
that the series of compounds of the metals of the alkaline earths with
hydrogen, nitrogen and carbon is a discovery of recent years, and that
probably further research will give rise to similar unexpected compounds,
and by extending our knowledge of their reactions prove to be of great
interest.
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