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6. Basic User-Defined Functions
6.1 Script files are just collections of MATLAB statements that are stored in a file. When a script file is
executed, the result is the same as it would be if all of the commands had been typed directly into
the Command Window. Script files share the Command Window’s workspace, so any variables that
were defined before the script file starts are visible to the script file, and any variables created by the
script file remain in the workspace after the script file finishes executing. A script file has no input
arguments and returns no results, but script files can communicate with other script files through the
data left behind in the workspace.

In contrast, MATLAB functions are a special type of M-file that run in their own independent
workspace. They receive input data through an input argument list, and return results to the caller
through an output argument list.

6.2 MATLAB programs communicate with their functions using a pass-by-value scheme. When a
function call occurs, MATLAB makes a copy of the actual arguments and passes them to the
function. This copying is very significant, because it means that even if the function modifies the
input arguments, it won’t affect the original data in the caller. Similarly, the returned values are
calculated by the function and copied into the return variables in the calling program.

6.3 The principal advantage of the pass-by-value scheme is that any changes to input arguments within a
function will not affect the input arguments in the calling program. This, along with the separate
workspace for the function, eliminates unintended side effects. The disadvantage is that copying
arguments, especially large arrays, can take time and memory.

6.4 A function to sort arrays in ascending or descending order, depending on the second calling
parameter, is shown below:

function out = ssort1(a,dir)

%SSORT1 Selection sort data in ascending or descending order
% Function SSORT1 sorts a numeric data set into ascending
% or descending order, depending on the value of the
% second parameter. If the parameter is 'up', then it
% sorts the data in ascending order. If the parameter is
% 'down', then it sorts the data in descending order. The
% default value is 'up'. Note that 'up' and 'down' may
% be abbreviated to 'u' and 'd', if desired.
%
% Note that the selection sort is relatively inefficient.
% DO NOT USE THIS FUNCTION FOR LARGE DATA SETS. Use MATLAB's
% "sort" function instead.

% Define variables:
% a -- Input array to sort
% ii -- Index variable
% iptr -- Pointer to min value
% jj -- Index variable
% nvals -- Number of values in "a"
% out -- Sorted output array
% temp -- Temp variable for swapping
129
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 % Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/03/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(1,2,nargin);
error(msg);

% If the direction argument is missing, set it to 'up'.

if nargin < 2
dir = 'up';
end

% Check for the direction of the sort

if dir(1) == 'u' | dir(1) == 'U'
sort_up = 1;
elseif dir(1) == 'd' | dir(1) == 'D'
sort_up = 0;
else
error('Second parameter is not ''UP'' or ''DOWN''!')
end

% Get the length of the array to sort

nvals = size(a,2);

% Sort the input array

for ii = 1:nvals-1

if sort_up

% Sort in ascending order.

% Find the minimum value in a(ii) through a(n)
iptr = ii;
for jj = ii+1:nvals
if a(jj) < a(iptr)
iptr = jj;
end
end

else

% Sort in descending order.

% Find the maximum value in a(ii) through a(n)
iptr = ii;
for jj = ii+1:nvals
if a(jj) < a(iptr)
iptr = jj;
end
end

end

130
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 % iptr now points to the min/max value, so swap a(iptr)
% with a(ii) if ii ~= iptr.
if ii ~= iptr
temp = a(ii);
a(ii) = a(iptr);
a(iptr) = temp;
end
end

% Pass data back to caller

out = a;

A script file to test this function is shown below:

% Script file: test_ssort1.m

%
% Purpose:
% To read in an input data set, sort it into ascending
% order using the selection sort algorithm, and to
% write the sorted data to the Command window. This
% program calls function "ssort1" to do the actual
% sorting.
%
% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/03/15 S. J. Chapman Original code
%
% Define variables:
% array -- Input data array
% ii -- Index variable
% nvals -- Number of input values
% sorted1 -- Sorted data array (up)
% sorted2 -- Sorted data array (down)

% Prompt for the number of values in the data set

nvals = input('Enter number of values to sort: ');

% Preallocate array
array = zeros(1,nvals);

% Get input values

for ii = 1:nvals

% Prompt for next value

string = ['Enter value ' int2str(ii) ': '];
array(ii) = input(string);

end

% Now sort the data in ascending order

sorted1 = ssort1(array,'up');

131
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 % Display the sorted result.
fprintf('\nSorted data in ascending order:\n');
for ii = 1:nvals
fprintf(' %8.4f\n',sorted1(ii));
end

% Now sort the data in descending order

sorted2 = ssort1(array,'down');

% Display the sorted result.

fprintf('\nSorted data in descending order:\n');
for ii = 1:nvals
fprintf(' %8.4f\n',sorted2(ii));
end

% Now sort the data in ascending order with

% no second argument.
sorted3 = ssort1(array);

% Display the sorted result.

fprintf('\nSorted data in default order:\n');
for ii = 1:nvals
fprintf(' %8.4f\n',sorted3(ii));
end

% The follwing call should produce an error message

sorted4 = ssort1(array,'bad');

When this program is executed, the results are:

» test_ssort1
Enter number of values to sort: 6
Enter value 1: -3
Enter value 2: 5
Enter value 3: 2
Enter value 4: 2
Enter value 5: 0
Enter value 6: 1

Sorted data in ascending order:

-3.0000
0.0000
1.0000
2.0000
2.0000
5.0000

Sorted data in descending order:

-3.0000
0.0000
1.0000
2.0000

132
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 2.0000
5.0000

Sorted data in default order:

-3.0000
0.0000
1.0000
2.0000
2.0000
5.0000
??? Error using ==> ssort1
Second parameter is not 'UP' or 'DOWN'!

Error in ==> C:\data\book\matlab_essentials\3e\soln\Ex5.4\test_ssort1.m

On line 66 ==>

6.5 A set of functions to perform trigonometric operations in degrees is shown below:

function out = sind(x)

%SIND Calculate sin(x), where x is in degrees
% Function SIND calculates sin(x), where x is in degrees
%
% Define variables:
% x -- Angle in degrees

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/03/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(1,1,nargin);
error(msg);

% Calculate value
out = sin(pi/180*x);

function out = sind(x)

%COSD Calculate cos(x), where x is in degrees
% Function COSD calculates cos(x), where x is in degrees
%
% Define variables:
% x -- Angle in degrees

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/03/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(1,1,nargin);
error(msg);

133
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 % Calculate value
out = cos(pi/180*x);

function out = tand(x)

%TAND Calculate tan(x), where x is in degrees
% Function TAND calculates tan(x), where x is in degrees
%
% Define variables:
% x -- Angle in degrees

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/03/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(1,1,nargin);
error(msg);

% Calculate value
out = tan(pi/180*x);

function out = asind(x)

%ASIND Calculate asin(x), where the output is in degrees
% Function ASIND calculates asin(x), where the output is in degrees
%
% Define variables:
% x -- Input value

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/03/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(1,1,nargin);
error(msg);

% Calculate value
out = 180/pi * asin(x);

function out = acosd(x)

%ACOSD Calculate acos(x), where the output is in degrees
% Function ACOSD calculates acos(x), where the output is in degrees
%
% Define variables:
% x -- Input value

% Record of revisions:

134
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 % Date Programmer Description of change
% ==== ========== =====================
% 04/03/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(1,1,nargin);
error(msg);

% Calculate value
out = 180/pi * acos(x);

function out = atand(x)

%ATAND Calculate atan(x), where the output is in degrees
% Function ATAND calculates atan(x), where the output is in degrees
%
% Define variables:
% x -- Input value

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/03/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(1,1,nargin);
error(msg);

% Calculate value
out = 180/pi * atan(x);

function out = atan2d(y,x)

%ATAN2D Four quadrant inverse tangent, where the output is in degrees
% Function ATAN2D calculates the Four quadrant inverse tangent, where
% the output is in degrees.
%
% Define variables:
% x -- Input value

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/03/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(2,2,nargin);
error(msg);

% Calculate value
out = 180/pi * atan2(y,x);

A script file to test these functions is given below:

135
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 % Script file: test_functions.m
%
% Purpose:
% To perform a median filter on an input data set.
%
% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/03/15 S. J. Chapman Original code
%
% Define variables:
% ii -- Loop index
% filename -- Input data file
% n_ave -- Number of points to average
% n_per_side -- Number of points to average per side
% n_points -- Number of points in data set
% slope -- Slope of the line
% x -- Array of input values
% y -- Array of filtered values

disp('This program tests the trig functions that return answers in

degrees.');

% Set the angle theta = 30 degrees, and try the forward trig functions
disp(' ');
disp(['Testing forward trig functions:']);
disp(['sind(30) = ' num2str(sind(30))]);
disp(['cosd(30) = ' num2str(cosd(30))]);
disp(['tand(30) = ' num2str(tand(30))]);
disp(['sind(45) = ' num2str(sind(45))]);
disp(['cosd(45) = ' num2str(cosd(45))]);
disp(['tand(45) = ' num2str(tand(45))]);

% Test the inverse trig functions

disp(' ');
disp(['Testing inverse trig functions:']);
disp(['asind(0) = ' num2str(asind(0))]);
disp(['asind(1/sqrt(2)) = ' num2str(asind(1/sqrt(2)))]);
disp(['asind(1) = ' num2str(asind(1))]);
disp(['acosd(0) = ' num2str(acosd(0))]);
disp(['acosd(1/sqrt(2)) = ' num2str(acosd(1/sqrt(2)))]);
disp(['acosd(1) = ' num2str(acosd(1))]);
disp(['atand(1) = ' num2str(atand(1))]);

% Test atan2d
disp(' ');
disp(['Testing atan2d:']);
disp(['atan2d(4,3) = ' num2str(atan2d(4,3))]);

When the script file is executed, the results are:

>> test_functions

136
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 This program tests the trig functions that return answers in degrees.

Testing forward trig functions:

sind(30) = 0.5
cosd(30) = 0.86603
tand(30) = 0.57735
sind(45) = 0.70711
cosd(45) = 0.70711
tand(45) = 1

Testing inverse trig functions:

asind(0) = 0
asind(1/sqrt(2)) = 45
asind(1) = 90
acosd(0) = 90
acosd(1/sqrt(2)) = 45
acosd(1) = 0
atand(1) = 45

Testing atan2d:
atan2d(4,3) = 53.1301

6.6 A function to convert degrees Fahrenheit to degrees Celsius is shown below:

function deg_c = f_to_c(deg_f)

%F_TO_C Convert degrees Fahrenheit to degrees Celsius
% Function F_TO_C converts degrees Fahrenheit to degrees Celsius
% %
% Calling sequence:
% deg_c = f_to_c(deg_f)

% Define variables:
% deg_f -- Input in degrees Fahrenheit
% deg_c -- Output in degrees Celsius

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/05/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(1,1,nargin);
error(msg);

% Calculate value
deg_c = 5/9 * (deg_f - 32);

We can test this function using the freezing and boiling points of water:

>> f_to_c(32)
ans =
0
>> f_to_c(212)

137
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 ans =
100

6.7 A function to convert degrees Celsius to degrees Fahrenheit is shown below:

function deg_f = c_to_f(deg_c)

%C_TO_F Convert degrees Celsius to degrees Fahrenheit
% Function C_TO_F converts degrees Celsius to degrees Fahrenheit
% %
% Calling sequence:
% deg_f = c_to_f(deg_c)

% Define variables:
% deg_c -- Input in degrees Celsius
% deg_f -- Output in degrees Fahrenheit

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/05/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(1,1,nargin);
error(msg);

% Calculate value
deg_f = 9/5 * deg_c + 32;

We can test this function using the freezing and boiling points of water:

>> f_to_f(0)
ans =
100
>> c_to_f(100)
ans =
0

We can also show that c_to_f and f_to_c are the inverses of each other:

>> f_to_c(c_to_f(30))
ans =
30

6.8 A function to calculate the area of a triangle specified by the locations of its three vertices is shown
below:

function area = area2d(x1, y1, x2, y2, x3, y3)

%AREA2D Calculate the area of a triangle specified by three vertices
% Function AREA2D calculates the area of a triangle specified by
% three vertices
%
% Calling sequence:
% area = area2d(x1, y1, x2, y2, x3, y3)

138
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 % Define variables:
% x1, y1 -- Location of vertex 1
% x2, y2 -- Location of vertex 2
% x3, y3 -- Location of vertex 3
% area -- Area of triangle

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/05/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(6,6,nargin);
error(msg);

% Calculate value
area = 0.5 * (x1*(y2-y3) - x2*(y1-y3) + x3*(y1-y2));

We can test this function using the specified points:

>> area = area2d(0,0,10,0,15,5)

area =
25.00

6.9 At this point in our studies, there is no general way to support an arbitrary number of arguments in a
function. Function nargin allows a developer to know how many arguments are used in a
function call, but only up to the number of arguments in the calling sequence1. We will design this
function to support up to 6 vertices. The corresponding function is shown below:

function area = area_polygon(x1, y1, x2, y2, x3, y3, x4, y4, x5, y5, x6, y6)
%AREA_POLYGON Calculate the area of a polygon specified by its vertices
% Function AREA_POLYGON calculates the area of a polygon specified by
% its vertices
%
% Calling sequence:
% area = area_polygon(x1, y1, x2, y2, x3, y3, x4, y4, x5, y5, x6, y6)

% Define variables:
% ii -- Loop index
% n_vertices -- Number of vetices in polygon
% x1, y1 -- Location of vertex 1
% x2, y2 -- Location of vertex 2
% x3, y3 -- Location of vertex 3
% x4, y4 -- Location of vertex 4
% x5, y5 -- Location of vertex 5
% x6, y6 -- Location of vertex 6
% area -- Area of polygon

% Record of revisions:
% Date Programmer Description of change

1 Later we will learn about function varargin, which can support any number of arguments.
139
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 % ==== ========== =====================
% 04/05/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

% There must be at least 3 vertices, and no more than 6.
msg = nargchk(6,12,nargin);
error(msg);

% Get the number of vertices

n_vertices = nargin / 2;

% Save vertices in arrays

x = zeros(1,n_vertices);
y = zeros(1,n_vertices);

% Save values
x(1) = x1;
y(1) = y1;
x(2) = x2;
y(2) = y2;
x(3) = x3;
y(3) = y3;
if n_vertices >= 4
x(4) = x4;
y(4) = y4;
end
if n_vertices >= 5
x(5) = x5;
y(5) = y5;
end
if n_vertices >= 6
x(6) = x6;
y(6) = y6;
end

% Calculate the area

area = 0;
for ii = 1:n_vertices-2
area = area + 0.5 * (x(ii)*(y(ii+1)-y(ii+2)) ...
- x(ii+1)*(y(ii)-y(ii+2)) ...
+ x(ii+2)*(y(ii)-y(ii+1)));
end

We can test this function using the specified point (0,0), (10,0), (10,10), and (0, 10), which
corresponds to a square with all sides having length 10:

>> area = area_polygon(0,0,10,0,10,10,0,10)

area =
100.00

We can test this function using the points specified in the problem:

>> area = area_polygon(0,0,10,0,10,10,0,10)

140
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 area =
100.00
>> area = area_polygon(10,0,8,8,2,10,-4,5)
area =
43.00

6.10 A function to calculate the inductance of a single-phase two-wire transmission line is shown below:

function ind = inductance(r, D, length)

%INDUCTANCE Calculate the inductance of a transmission line
% Function INDUCTANCE calculates the inductance of a
% single-phase two-wire transmission line.
%
% Calling sequence:
% ind = inductance(r, D, length)
%
% where
% r = the radius of the conductors in meters
% D = the distance between the two lines in meters
% length = Length of transmission line in meters

% Define variables:
% ind_per_m -- Inductance per meter

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/05/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(3,3,nargin);
error(msg);

% Constants
mu0 = pi * 4e-7; % H/m

% Calculate the inductance

ind_per_m = mu0 / pi * (1/4 + log(D/r));

% Get the inductance

ind = ind_per_m * length;

We can test this function using the points specified in the problem:

>> ind = inductance(0.02, 1.5, 100000)

ind =
0.1827

6.11 If the diameter of a transmission line’s conductors increase, the inductance of the line will decrease.
If the diameter of the conductors are doubled, the inductance will fall to:

>> ind = inductance(0.02, 1.5, 100000)

ind =

141
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 0.1550

6.12 A function to calculate the capacitance of a single-phase two-wire transmission line is shown below:

function cap = capacitance(r, D, length)

%CAPACITANCE Calculate the capacitance of a transmission line
% Function CAPACITANCE calculates the capacitance of a
% single-phase two-wire transmission line.
%
% Calling sequence:
% cap = capacitance(r, D, length)
%
% where
% r = the radius of the conductors in meters
% D = the distance between the two lines in meters
% length = Length of transmission line in meters

% Define variables:
% cap_per_m -- Capacitance per meter

% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/05/15 S. J. Chapman Original code

% Check for a legal number of input arguments.

msg = nargchk(3,3,nargin);
error(msg);

% Constants
e0 = pi * 4e-7; % F/m

% Calculate the capacitance

cap_per_m = pi * e0 / log((D-r)/r);

% Get the capacitance

cap = cap_per_m * length;

We can test this function using the points specified in the problem:

>> cap = capacitance(0.04, 1.5, 100000)

cap =
0.1097

6.13 If the distance between the two conductors increases, the inductance of the transmission line
increases and the capacitance of the transmission line decreases.

6.14 A program to compare the sorting times using the selection sort of Example 6.2 and MATLAB’s
built-in sort is shown below:

% Script file: compare_sorts.m

%
% Purpose:

142
© 2018 Cengage Learning®. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
 % To compare the sort function from Example 6.2 and the
% built-in MATLAB sort
%
% Record of revisions:
% Date Programmer Description of change
% ==== ========== =====================
% 04/05/15 S. J. Chapman Original code
%
% Define variables:
% data1 -- Array to sort
% data2 -- Copy of array to sort
% elapsed_time1 -- Elapsed time for ssort
% elapsed_time2 -- Elapsed time for sort

% Constants
SIZE = 100000; % Number of values to sort

% Set seed
seed(123456);

% Create a sample data set to sort.

data1 = random0(1,SIZE);

% Sort using ssort

data2 = data1;
tic;
out = ssort(data2);
elapsed_time1 = toc;

% Sort using sort

data2 = data1;
tic;
out = sort(data2);
elapsed_time2 = toc;

% Display the relative times

disp(['Sort time using ssort = ' num2str(elapsed_time1)]);
disp(['Sort time using sort = ' num2str(elapsed_time2)]);

When this program is executed, the results are:

>> compare_sorts
Sort time using ssort = 71.2407
Sort time using sort = 0.0060984

The built-in sorting function is dramatically faster than the selection sort of Example 6.2.

6.15 A program to compare the sorting times using the selection sort of Example 6.2 and MATLAB’s
built-in sort is shown below.

% Script file: compare_sorts.m

%
% Purpose:

143
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Title: The Principles of Chemistry, Volume II

Author: Dmitry Ivanovich Mendeleyev

Editor: T. A. Lawson

Translator: George Kamensky

Release date: February 19, 2017 [eBook #54210]

Most recently updated: October 23, 2024

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*** START OF THE PROJECT GUTENBERG EBOOK THE PRINCIPLES OF CHEMISTRY, VOLUME II ***
 THE
PRINCIPLES OF CHEMISTRY
By D. MENDELÉEFF

TRANSLATED FROM THE RUSSIAN (SIXTH EDITION) BY

GEORGE KAMENSKY, A.R.S.M.

OF THE IMPERIAL MINT, ST PETERSBURG: MEMBER OF THE RUSSIAN
PHYSICO-CHEMICAL SOCIETY

EDITED BY

T. A. LAWSON, B.Sc. Ph.D.

EXAMINER IN COAL-TAR PRODUCTS TO THE CITY AND GUILDS OF LONDON
INSTITUTE FELLOW OF THE INSTITUTE OF CHEMISTRY

IN TWO VOLUMES
VOLUME II.

LONGMANS, GREEN, AND CO

39 PATERNOSTER ROW, LONDON
NEW YORK AND BOMBAY
1897

All rights reserved

Table III.
The periodic dependence of the composition of the simplest compounds and
properties of the simple bodies upon the atomic weights of the elements.
 Molecular
composition of the
higher hydrogen Atomic weights of the
Composition of the saline com
and elements
metallo-organic
compounds
Br, (NO3), ½O, ½(SO4), OH, (OM
½Ca, ⅓Al, &c.
E=CH3, C2H5, &c. Form RX RX2 RX3 RX4 RX5
Oxides R2O RO R2O3 RO2 R2O5

[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11]

HX
HH H (mean) or
1,005
H2 O

Li 7·02 (Stas) LiX

(Nilson
Be 9·1 — BX2
Pettersson)
(Ramsay
BE3 — — B 11·0 — — BX3
Ashton)
CH4 C2H6 C2H4 C2H2 C 12·0 (Roscoe) — CO — COZ2
NH3 N2H4 — N 14·04 (Stas) N2O NO NOZ NO2 NO2Z
OH2 — O 16 (conventional) — OX2
— FH F 19·0 (Christiansen) FZ —

NaE Na 23·04 (Stas) NaX

MgE2 — Mg 24·3 (Burton) — MgX2
AlE3 — — Al 27·1 (Mallet) — — AlX3
(Thorpe
SiH4 Si2E6 — — Si 28·4 — — — SiOZ2
Young)
PH3 P2H4 — P 31·0 (v. d. Plaats) — — PX3 — POZ3
SH2 — S 32·06 (Stas) — SX2 — SOZ2 —
ClH Cl 35·45 (Stas) ClZ — ClOZ — ClO2Z
 K 39·15 (Stas) KX
Ca 40·0 (Dumas) — CaX2
Sc 44·0 (Nilson) — — ScX3
Ti 48·1 (Thorpe) — TiX2 TiX3 TiX4
V 51·2 (Roscoe) — VO VOX — VOZ3
Cr 52·1 (Rawson) — CrX2 CrX3 CrO2 —
Mn 55·1 (Marignac) — MnX2 MnX3 MnO2 — M
Fe 56·0 (Dumas) — FeX2 FeX3 — —
Co 58·9 (Zimmermann) — CoX2 CoX3 CoO2
Ni 59·4 (Winkler) — NiX2 NiX3
Cu 63·6 (Richards) CuX CuX2
ZnE2 — Zn 65·3 (Marignac) — ZnX2
GaE3 — — Ga 69·9 (Boisbaudran) — — GaX3
GeE4 — — — Ge 72·3 (Winkler) — GaX2 — GaX4
AsH3 — — As 75·0 (Dumas) — AsS AsX3 AsS2 AsO2Z
SeH2 — Se 79·0[A] (Pettersson) — — — SeOZ2 —
BrH Br 79·95 (Stas) BrZ — BrOZ — BrO2Z

Rb 85·5 (Godeffroy) RbX

Sr 87·6 (Dumas) — SrX2
Y 89 (Clève) — — YX3
Zr 90·6 (Bailey) — — — ZrX4
Nb 94 (Marignac) — — NbX3 — NbO2Z
Mo 96·1 (Maas) — — MoX3 MoX4 — M
Unknown metal (eka-manganese, Em = 99).
Ru 101·7 (Joly) — RuX2 RuX3 RuX4 —
Rh 102·7 (Seubert) — RhX2 RhX3 RhX4 —
Pd 106·4 (Keller Smith) PdX PdX2 — PdX4
Ag 107·92 (Stas) AgX
(Lorimer
CdE2 — Cd 112·1 — CdX2
Smith)
InE3 — — In 113·6 (Winkler) — InX2 InX3
SnE4 — — — Sn 119·1 (Classen) — SnX2 — SnX4
SbH3 — — Sb 120·4 (Schneider) — — SbX3 — SbO2Z
 TeH2 — Te 125·1 (Brauner) — — — TeOZ2
IH I 126·85 (Stas) IZ — IZ3 — IO2Z

Cs 132·7 (Godeffroy) CsX

Ba 137·4 (Richards) — BaX2
La 138·2 (Brauner) — — LaX3
Ce 140·2 (Brauner) — — CeX3 CeX4
Little known Di = 142.1 and Yb = 173.2, and over 15 unknown elemen
Ta 182·7 (Marignac) — — — — TaO2Z
W 184·0 (Waddel) — — — WX4 —
Unknown element.
Os 191·6 (Seubert) — — OsX3 OsX4 —
Ir 193·3 (Joly) — — IrX3 IrX4 —
(Dittmar
Pt 196·0 — PtX2 — PtX4
McArthur)
(Dittmar
Au 197·5 AuX — AuX3
McArthur)
(Erdmann
HgE2 — Hg 200·5 HgX HgX2
Mar.)
TlE3 — — Tl 204·1 (Crookes) TlX — TlX3
PbE4 — — — Pb 206·90 (Stas) — PbX2 — PbOZ2
BiE3 — — Bi 208·9 (Classen) — — BiX3 — BiO2
Five unknown elements.
Th 232·4 (Krüss Nilson) — — — ThX4
Unknown element.
U 239·3 (Zimmermann) — — — UO2 —
[A] From analogy there is reason for thinking that the atomic weight of selenium is really slightly less
than 79·0.

Columns 1, 2, 3, and 4 give the molecular composition of the hydrogen and

metallo-organic compounds, exhibiting the most characteristic forms assumed
by the elements. The first column contains only those which correspond to the
form RX4, the second column those of the form RX3, the third of the form RX2,
and the fourth of the form RX, so that the periodicity stands out clearly (see
Column 16).
Column 5 contains the symbols of all the more or less well-known elements,
placed according to the order of the magnitude of their atomic weights.
 Column 6 contains the atomic weights of the elements according to the most
trustworthy determinations. The names of the investigators are given in
parenthesis. The atomic weight of oxygen, taken as 16, forms the basis upon
which these atomic weights were calculated. Some of these have been
recalculated by me on the basis of Stas's most trustworthy data (see Chapter
XXIV. and the numbers given by Stas in the table, where they are taken
according to van der Plaats and Thomsen's calculations).
Columns 7–14 contain the composition of the saline compounds of the
elements, placed according to their forms, RX, RX2 to RX8 (in the 14th column).
If the element R has a metallic character like H, Li, Be, &c., then X represents Cl,
NO3, ½ SO4, &c., haloid radicles, or (OH) if a perfect hydrate is formed (alkali,
aqueous base), or ½ O, ½ S, &c. when an anhydrous oxide, sulphide, &c. is
formed. For instance, NaCl, Mg(NO3)2, Al2(SO4)3, correspond to NaX, MgX2, and
AlX3; so also Na(OH), Mg(OH)2, Al(OH)3, Na2O, MgO, Al2O3, &c. But if the
element, like C or N, be of a metalloid or acid character, X must be regarded as
(OH) in the formation of hydrates; (OM) in the formation of salts, where M is the
equivalent of a metal, ½ O in the formation of an anhydride, and Cl in the
formation of a chloranhydride; and in this case (i.e. in the acid compounds) Z is
put in the place of X; for example, the formulæ COZ2, NO2Z, MNO2Z, FeO2Z2,
and IZ3 correspond to CO(NaO)2 = Na2CO3, COCl2, CO2, NO2(NaO) = NaNO3,
NO2Cl, NO2(OH) = HNO3; MnO3(OK) = KMnO4, ICl, &c.
The 15th column gives the compositions of the peroxides of the elements,
taking them as anhydrous. An asterisk (*) is attached to those of which the
composition has not been well established, and a dash (—) shows that for a
given element no peroxides have yet been obtained. The peroxides contain
more oxygen than the higher saline oxides of the same elements, are powerfully
oxidising, and easily give peroxide of hydrogen. This latter circumstance
necessitates their being referred to the type of peroxide of hydrogen, if bases
and acids are referred to the type of water (see Chapter XV., Note 7 and 11 bis).
The 16th column gives the composition of the lower hydrogen compounds like
N3H and Na2H. They may often be regarded as alloys of hydrogen, which is
frequently disengaged by them at a comparatively moderate temperature. They
differ greatly in their nature from the hydrogen compounds given in columns 1–
4 (see Note 12).
Column 17 gives the specific gravity of the elements in a solid and a liquid
state. An asterisk (*) is placed by those which can either only be assumed from
analogy (for example, the sp. gr. of fluorine and hydrogen, which have not been
obtained in a liquid state), or which vary very rapidly with a variation of
temperature and pressure (like oxygen and nitrogen), or physical state (for
instance, carbon in passing from the state of charcoal to graphite and diamond).
But as the sp. gr. in general varies with the temperature, mechanical condition,
&c., the figures given, although chosen from the most trustworthy sources, can
only be regarded as approximate, and not as absolutely true. They clearly show
a certain periodicity; for instance, the sp. gr. diminishes from Al on both sides
(Al, Mg, Na, with decreasing atomic weight; and Al, Si, P, S, Cl, with increasing
atomic weight, it also diminishes on both sides from Cu, Ru, and Os.)
The same remarks refer to the figures in the 18th column, which gives the so-
called atomic volumes of the simple bodies, or the quotient of their atomic
weight and specific gravity. For Na, K, Rb, and Cs the atomic volume is greatest
among the neighbouring elements. For Ni, Pd, and Os it is least, and this
indicates the periodicity of this property of the simple bodies.
The last (19th) column gives the melting points of the simple bodies. Here
also a periodicity is seen, i.e. a maximum and minimum value between which
there are intermediate values, as we see, for instance, in the series Cl, K, Ca, Sc,
and Ti, or in the series Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Ge.
 PRINCIPLES OF CHEMISTRY

CHAPTER XV

THE GROUPING OF THE ELEMENTS AND THE PERIODIC LAW

It is seen from the examples given in the preceding chapters that the sum of
the data concerning the chemical transformations proper to the elements (for
instance, with respect to the formation of acids, salts, and other compounds
having definite properties) is insufficient for accurately determining the
relationship of the elements, inasmuch as this may be many-sided. Thus, lithium
and barium are in some respects analogous to sodium and potassium, and in
others to magnesium and calcium. It is evident, therefore, that for a complete
judgment it is necessary to have, not only qualitative, but also quantitative,
exact and measurable, data. When a property can be measured it ceases to be
vague, and becomes quantitative instead of merely qualitative.
Among these measurable properties of the elements, or of their corresponding
compounds, are: (a) isomorphism, or the analogy of crystalline forms; and,
connected with it, the power to form crystalline mixtures which are
isomorphous; (b) the relation of the volumes of analogous compounds of the
elements; (c) the composition of their saline compounds; and (d) the relation of
the atomic weights of the elements. In this chapter we shall briefly consider
these four aspects of the matter, which are exceedingly important for a natural
and fruitful grouping of the elements, facilitating, not only a general
acquaintance with them, but also their detailed study.
Historically the first, and an important and convincing, method for finding a
relationship between the compounds of two different elements is by
isomorphism. This conception was introduced into chemistry by Mitscherlich (in
1820), who demonstrated that the corresponding salts of arsenic acid, H3AsO4,
and phosphoric acid, H3PO4, crystallise with an equal quantity of water, show an
exceedingly close resemblance in crystalline form (as regards the angles of their
faces and axes), and are able to crystallise together from solutions, forming
crystals containing a mixture of the isomorphous compounds. Isomorphous
substances are those which, with an equal number of atoms in their molecules,
present an analogy in their chemical reactions, a close resemblance in their
properties, and a similar or very nearly similar crystalline form: they often
contain certain elements in common, from which it is to be concluded that the
remaining elements (as in the preceding example of As and P) are analogous to
each other. And inasmuch as crystalline forms are capable of exact
measurement, the external form, or the relation of the molecules which causes
their grouping into a crystalline form, is evidently as great a help in judging of
the internal forces acting between the atoms as a comparison of reactions,
vapour densities, and other like relations. We have already seen examples of this
in the preceding pages.[1] It will be sufficient to call to mind that the compounds
of the alkali metals with the halogens RX, in a crystalline form, all belong to the
cubic system and crystallise in octahedra or cubes—for example, sodium
chloride, potassium chloride, potassium iodide, rubidium chloride, &c. The
nitrates of rubidium and cæsium appear in anhydrous crystals of the same form
as potassium nitrate. The carbonates of the metals of the alkaline earths are
isomorphous with calcium carbonate—that is, they either appear in forms like
calc spar or in the rhombic system in crystals analogous to aragonite.[1 bis]
Furthermore, sodium nitrate crystallises in rhombohedra, closely resembling the
rhombohedra of calc spar (calcium carbonate), CaCO3, whilst potassium nitrate
appears in the same form as aragonite, CaCO3, and the number of atoms in
both kinds of salts is the same: they all contain one atom of a metal (K, Na, Ca),
one atom of a non-metal (C, N), and three atoms of oxygen. The analogy of
form evidently coincides with an analogy of atomic composition. But, as we have
learnt from the previous description of these salts, there is not any close
resemblance in their properties. It is evident that calcium carbonate approaches
more nearly to magnesium carbonate than to sodium nitrate, although their
crystalline forms are all equally alike. Isomorphous substances which are
perfectly analogous to each other are not only characterised by a close
resemblance of form (homeomorphism), but also by the faculty of entering into
analogous reactions, which is not the case with RNO3 and RCO3. The most
important and direct method of recognising perfect isomorphism—that is, the
absolute analogy of two compounds—is given by that property of analogous
compounds of separating from solutions in homogeneous crystals, containing
the most varied proportions of the analogous substances which enter into their
composition. These quantities do not seem to be in dependence on the
molecular or atomic weights, and if they are governed by any laws they must be
analogous to those which apply to indefinite chemical compounds.[2] This will be
clear from the following examples. Potassium chloride and potassium nitrate are
not isomorphous with each other, and are in an atomic sense composed in a
different manner. If these salts be mixed in a solution and the solution be
evaporated, independent crystals of the two salts will separate, each in that
crystalline form which is proper to it. The crystals will not contain a mixture of
the two salts. But if we mix the solutions of two isomorphous salts together,
then, under certain circumstances, crystals will be obtained which contain both
these substances. However, this cannot be taken as an absolute rule, for if we
take a solution saturated at a high temperature with a mixture of potassium and
sodium chlorides, then on evaporation sodium chloride only will separate, and
on cooling only potassium chloride. The first will contain very little potassium
chloride, and the latter very little sodium chloride.[3] But if we take, for example,
a mixture of solutions of magnesium sulphate and zinc sulphate, they cannot be
separated from each other by evaporating the mixture, notwithstanding the
rather considerable difference in the solubility of these salts. Again, the
isomorphous salts, magnesium carbonate, and calcium carbonate are found
together—that is, in one crystal—in nature. The angle of the rhombohedron of
these magnesia-lime spars is intermediate between the angles proper to the two
spars individually (for calcium carbonate, the angle of the rhombohedron is 105°
8′; magnesium carbonate, 107° 30′; CaMg(CO3)2, 106° 10′). Certain of these
isomorphous mixtures of calc and magnesia spars appear in well-formed
crystals, and in this case there not unfrequently exists a simple molecular
proportion of strictly definite chemical combination between the component salts
—for instance, CaCO3,MgCO3—whilst in other cases, especially in the absence of
distinct crystallisation (in dolomites), no such simple molecular proportion is
observable: this is also the case in many artificially prepared isomorphous
mixtures. The microscopical and crystallo-optical researches of Professor
Inostrantzoff and others show that in many cases there is really a mechanical,
although microscopically minute, juxtaposition in one whole of the
heterogeneous crystals of calcium carbonate (double refracting) and of the
compound CaMgC2O6. If we suppose the adjacent parts to be microscopically
small (on the basis of the researches of Mallard, Weruboff, and others), we
obtain an idea of isomorphous mixtures. A formula of the following kind is given
to isomorphous mixtures: for instance, for spars, RCO3, where R = Mg, Ca, and
where it may be Fe,Mn …, &c. This means that the Ca is partially replaced by Mg
or another metal. Alums form a common example of the separation of
isomorphous mixtures from solutions. They are double sulphates (or seleniates)
of alumina (or oxides isomorphous with it) and the alkalis, which crystallise in
well-formed crystals. If aluminium sulphate be mixed with potassium sulphate,
an alum separates, having the composition KAlS2O8,12H2O. If sodium sulphate
or ammonium sulphate, or rubidium (or thallium) sulphate be used, we obtain
alums having the composition RAlS2O8,12H2O. Not only do they all crystallise in
the cubic system, but they also contain an equal atomic quantity of water of
crystallisation (12H2O). Besides which, if we mix solutions of the potassium and
ammonium (NH4AlS2O8,12H2O) alums together, then the crystals which separate
will contain various proportions of the alkalis taken, and separate crystals of the
alums of one or the other kind will not be obtained, but each separate crystal
will contain both potassium and ammonium. Nor is this all; if we take a crystal
of a potassium alum and immerse it in a solution capable of yielding ammonia
alum, the crystal of the potash alum will continue to grow and increase in size in
this solution—that is, a layer of the ammonia or other alum will deposit itself
upon the planes bounding the crystal of the potash alum. This is very distinctly
seen if a colourless crystal of a common alum be immersed in a saturated violet
solution of chrome alum, KCrS2O8,12H2O, which then deposits itself in a violet
layer over the colourless crystal of the alumina alum, as was observed even
before Mitscherlich noticed it. If this crystal be then immersed in a solution of an
alumina alum, a layer of this salt will form over the layer of chrome alum, so
that one alum is able to incite the growth of the other. If the deposition proceed
simultaneously, the resultant intermixture may be minute and inseparable, but
its nature is understood from the preceding experiments; the attractive force of
crystallisation of isomorphous substances is so nearly equal that the attractive
power of an isomorphous substance induces a crystalline superstructure exactly
the same as would be produced by the attractive force of like crystalline
particles. From this it is evident that one isomorphous substance may induce the
crystallisation[4] of another. Such a phenomenon explains, on the one hand, the
aggregation of different isomorphous substances in one crystal, whilst, on the
other hand, it serves as a most exact indication of the nearness both of the
molecular composition of isomorphous substances and of those forces which are
proper to the elements which distinguish the isomorphous substances. Thus, for
example, ferrous sulphate or green vitriol crystallises in the monoclinic system
and contains seven molecules of water, FeSO4,7H2O, whilst copper vitriol
crystallises with five molecules of water in the triclinic system, CuSO4,5H2O;
nevertheless, it may be easily proved that both salts are perfectly isomorphous;
that they are able to appear in identically the same forms and with an equal
molecular amount of water. For instance, Marignac, by evaporating a mixture of
sulphuric acid and ferrous sulphate under the receiver of an air-pump, first
obtained crystals of the hepta-hydrated salt, and then of the penta-hydrated salt
FeSO4,5H2O, which were perfectly similar to the crystals of copper sulphate.
Furthermore, Lecoq de Boisbaudran, by immersing crystals of FeSO4,7H2O in a
supersaturated solution of copper sulphate, caused the latter to deposit in the
same form as ferrous sulphate, in crystals of the monoclinic system,
CuSO4,7H2O.
Hence it is evident that isomorphism—that is, the analogy of forms and the
property of inducing crystallisation—may serve as a means for the discovery of
analogies in molecular composition. We will take an example in order to render
this clear. If, instead of aluminium sulphate, we add magnesium sulphate to
potassium sulphate, then, on evaporating the solution, the double salt
K2MgS2O8,6H2O (Chapter XIV., Note 28) separates instead of an alum, and the
ratio of the component parts (in alums one atom of potassium per 2SO4, and
here two atoms) and the amount of water of crystallisation (in alums 12, and
here 6 equivalents per 2SO4) are quite different; nor is this double salt in any
way isomorphous with the alums, nor capable of forming an isomorphous
crystalline mixture with them, nor does the one salt provoke the crystallisation
of the other. From this we must conclude that although alumina and magnesia,
or aluminium and magnesium, resemble each other, they are not isomorphous,
and that although they give partially similar double salts, these salts are not
analogous to each other. And this is expressed in their chemical formulæ by the
fact that the number of atoms in alumina or aluminium oxide, Al2O3, is different
from the number in magnesia, MgO. Aluminium is trivalent and magnesium
bivalent. Thus, having obtained a double salt from a given metal, it is possible to
judge of the analogy of the given metal with aluminium or with magnesium, or
of the absence of such an analogy, from the composition and form of this salt.
Thus zinc, for example, does not form alums, but forms a double salt with
potassium sulphate, which has a composition exactly like that of the
corresponding salt of magnesium. It is often possible to distinguish the bivalent
metals analogous to magnesium or calcium from the trivalent metals, like
aluminium, by such a method. Furthermore, the specific heat and vapour density
serve as guides. There are also indirect proofs. Thus iron gives ferrous
compounds, FeX2, which are isomorphous with the compounds of magnesium,
and ferric compounds, FeX3, which are isomorphous with the compounds of
aluminium; in this instance the relative composition is directly determined by
analysis, because, for a given amount of iron, FeCl2 only contains two-thirds of
the amount of chlorine which occurs in FeCl3, and the composition of the
corresponding oxygen compounds, i.e. of ferrous oxide, FeO, and ferric oxide,
Fe2O3, clearly indicates the analogy of the ferrous oxide with MgO and of the
ferric oxide with Al2O3.
Thus in the building up of similar molecules in crystalline forms we see one of
the numerous means for judging of the internal world of molecules and atoms,
and one of the weapons for conquests in the invisible world of molecular
mechanics which forms the main object of physico-chemical knowledge. This
method[5] has more than once been employed for discovering the analogy of
elements and of their compounds; and as crystals are measurable, and the
capacity to form crystalline mixtures can be experimentally verified, this method
is a numerical and measurable one, and in no sense arbitrary.
The regularity and simplicity expressed by the exact laws of crystalline form
repeat themselves in the aggregation of the atoms to form molecules. Here, as
there, there are but few forms which are essentially different, and their apparent
diversity reduces itself to a few fundamental differences of type. There the
molecules aggregate themselves into crystalline forms; here, the atoms
aggregate themselves into molecular forms or into the types of compounds. In
both cases the fundamental crystalline or molecular forms are liable to
variations, conjunctions, and combinations. If we know that potassium gives
compounds of the fundamental type KX, where X is a univalent element (which
combines with one atom of hydrogen, and is, according to the law of
substitution, able to replace it), then we know the composition of its
compounds: K2O, KHO, KCl, NH2K, KNO3, K2SO4, KHSO4, K2Mg(SO4)2,6H2O, &c.
All the possible derivative crystalline forms are not known. So also all the atomic
combinations are not known for every element. Thus in the case of potassium,
KCH3, K3P, K2Pt, and other like compounds which exist for hydrogen or chlorine,
are unknown.
Only a few fundamental types exist for the building up of atoms into
molecules, and the majority of them are already known to us. If X stand for a
univalent element, and R for an element combined with it, then eight atomic
types may be observed:—
RX, RX2, RX3, RX4, RX5, RX6, RX7, RX8.
Let X be chlorine or hydrogen. Then as examples of the first type we have: H2,
Cl2, HCl, KCl, NaCl, &c. The compounds of oxygen or calcium may serve as
examples of the type RX2: OH2, OCl2, OHCl, CaO, Ca(OH)2, CaCl2, &c. For the
third type RX3 we know the representative NH3 and the corresponding
compounds N2O3, NO(OH), NO(OK), PCl3, P2O3, PH3, SbH3, Sb2O3, B2O3, BCl3,
Al2O3, &c. The type RX4 is known among the hydrogen compounds. Marsh gas,
CH4, and its corresponding saturated hydrocarbons, CnH2n+2, are the best
representatives. Also CH3Cl, CCl4, SiCl4, SnCl4, SnO2, CO2, SiO2, and a whole
series of other compounds come under this class. The type RX5 is also already
familiar to us, but there are no purely hydrogen compounds among its
representatives. Sal-ammoniac, NH4Cl, and the corresponding NH4(OH),
NO2(OH), ClO2(OK), as well as PCl5, POCl3, &c., are representatives of this type.
In the higher types also there are no hydrogen compounds, but in the type RX6
there is the chlorine compound WCl6. However, there are many oxygen
compounds, and among them SO3 is the best known representative. To this
class also belong SO2(OH)2, SO2Cl2, SO2(OH)Cl, CrO3, &c., all of an acid
character. Of the higher types there are in general only oxygen and acid
representatives. The type RX7 we know in perchloric acid, ClO3(OH), and
 potassium permanganate, MnO3(OK), is also a member. The type RX8 in a free
state is very rare; osmic anhydride, OsO4, is the best known representative of it.
[6]

The four lower types RX, RX2, RX3, and RX4 are met with in compounds of the
elements R with chlorine and oxygen, and also in their compounds with
hydrogen, whilst the four higher types only appear for such acid compounds as
are formed by chlorine, oxygen, and similar elements.
Among the oxygen compounds the saline oxides which are capable of forming
salts either through the function of a base or through the function of an acid
anhydride attract the greatest interest in every respect. Certain elements, like
calcium and magnesium, only give one saline oxide—for example, MgO,
corresponding with the type MgX2. But the majority of the elements appear in
several such forms. Thus copper gives CuX and CuX2, or Cu2O and CuO. If an
element R gives a higher type RXn, then there often also exist, as if by
symmetry, lower types, RXn-2, RXn-4, and in general such types as differ from RXn
by an even number of X. Thus in the case of sulphur the types SX2, SX4, and SX6
are known—for example SH2, SO2, and SO3. The last type is the highest, SX6.
The types SX5 and SX3 do not exist. But even and uneven types sometimes
appear for one and the same element. Thus the types RX and RX2 are known for
copper and mercury.
Among the saline oxides only the eight types enumerated below are known to
exist. They determine the possible formulæ of the compounds of the elements,
if it be taken into consideration that an element which gives a certain type of
combination may also give lower types. For this reason the rare type of the
suboxides or quaternary oxides R4O (for instance, Ag4O, Ag2Cl) is not
characteristic; it is always accompanied by one of the higher grades of oxidation,
and the compounds of this type are distinguished by their great chemical
instability, and split up into an element and the higher compound (for instance,
Ag4O = 2Ag + Ag2O). Many elements, moreover, form transition oxides whose
composition is intermediate, which are able, like N2O4, to split up into the lower
and higher oxides. Thus iron gives magnetic oxide, Fe3O4, which is in all respects
(by its reactions) a compound of the suboxide FeO with the oxide Fe2O3. The
independent and more or less stable saline compounds correspond with the
following eight types :—
R2O; salts RX, hydroxides ROH. Generally basic like K2O, Na2O, Hg2O, Ag2O,
Cu2O; if there are acid oxides of this composition they are very rare, are only
 formed by distinctly acid elements, and even then have only feeble acid
properties; for example, Cl2O and N2O.
R2O2 or RO; salts RX2, hydroxides R(OH)2. The most simple basic salts R2OX2 or
R(OH)X; for instance, the chloride Zn2OCl2; also an almost exclusively basic
type; but the basic properties are more feebly developed than in the preceding
type. For example, CaO, MgO, BaO, PbO, FeO, MnO, &c.
R2O3; salts RX3, hydroxides R(OH)3, RO(OH), the most simple basic salts ROX,
R(OH)X3. The bases are feeble, like Al2O3, Fe2O3, Tl2O3, Sb2O3. The acid
properties are also feebly developed; for instance, in B2O3; but with the non-
metals the properties of acids are already clear; for instance, P2O3, P(OH)3.
R2O4 or RO2; salts RX4 or ROX2, hydroxides R(OH)4, RO(OH)2. Rarely bases
(feeble), like ZrO2, PtO2; more often acid oxides; but the acid properties are in
general feeble, as in CO2, SO2, SnO2. Many intermediate oxides appear in this
and the preceding and following types.
R2O5; salts principally of the types ROX3, RO2X, RO(OH)3, RO2(OH), rarely RX5.
The basic character (X, a halogen, simple or complex; for instance, NO3, Cl,
&c.) is feeble; the acid character predominates, as is seen in N2O5, P2O5,
Cl2O5; then X = OH, OK, &c., for example NO2(OK).
R2O6 or RO3; salts and hydroxides generally of the type RO2X2, RO2(OH)2. Oxides
of an acid character, as SO3, CrO3, MnO3. Basic properties rare and feebly
developed as in UO3.
R2O7; salts of the form RO3X, RO3(OH), acid oxides; for instance, Cl2O7, Mn2O7.
Basic properties as feebly developed as the acid properties in the oxides R2O.
R2O8 or RO4. A very rare type, and only known in OsO4 and RuO4.
It is evident from the circumstance that in all the higher types the acid
hydroxides (for example, HClO4, H2SO4, H3PO4) and salts with a single atom of
one element contain, like the higher saline type RO4, not more than four atoms
of oxygen; that the formation of the saline oxides is governed by a certain
common principle which is best looked for in the fundamental properties of
oxygen, and in general of the most simple compounds. The hydrate of the oxide
RO2 is of the higher type RO22H2O = RH4O4 = R(HO)4. Such, for example, is the
hydrate of silica and the salts (orthosilicates) corresponding with it, Si(MO)4. The
oxide R2O5, corresponds with the hydrate R2O53H2O = 2RH3O4 = 2RO(OH)3.
Such is orthophosphoric acid, PH3O3. The hydrate of the oxide RO3 is RO3H2O =
RH2O4 = RO2(OH)2—for instance, sulphuric acid. The hydrate corresponding to
R2O7 is evidently RHO = RO3(OH)—for example, perchloric acid. Here, besides
containing O4, it must further be remarked that the amount of hydrogen in the
hydrate is equal to the amount of hydrogen in the hydrogen compound. Thus
silicon gives SiH4 and SiH4O4, phosphorus PH3 and PH3O4, sulphur SH2 and
SH2O4, chlorine ClH and ClHO4. This, if it does not explain, at least connects in a
harmonious and general system the fact that the elements are capable of
combining with a greater amount of oxygen, the less the amount of hydrogen
which they are able to retain. In this the key to the comprehension of all further
deductions must be looked for, and we will therefore formulate this rule in
general terms. An element R gives a hydrogen compound RHn, the hydrate of its
higher oxide will be RHnO4, and therefore the higher oxide will contain 2RHnO4 -
nH2O = R2O8 - n. For example, chlorine gives ClH, hydrate ClHO4, and the higher
oxide Cl2O7. Carbon gives CH4 and CO2. So also, SiO2 and SiH4 are the higher
compounds of silicon with hydrogen and oxygen, like CO2 and CH4. Here the
amounts of oxygen and hydrogen are equivalent. Nitrogen combines with a
large amount of oxygen, forming N2O5, but, on the other hand, with a small
quantity of hydrogen in NH3. The sum of the equivalents of hydrogen and
oxygen, occurring in combination with an atom of nitrogen, is, as always in the
higher types, equal to eight. It is the same with the other elements which
combine with hydrogen and oxygen. Thus sulphur gives SO3; consequently, six
equivalents of oxygen fall to an atom of sulphur, and in SH2 two equivalents of
hydrogen. The sum is again equal to eight. The relation between Cl2O7 and ClH
is the same. This shows that the property of elements of combining with such
different elements as oxygen and hydrogen is subject to one common law,
which is also formulated in the system of the elements presently to be
described.[7]
In the preceding we see not only the regularity and simplicity which govern
the formation and properties of the oxides and of all the compounds of the
elements, but also a fresh and exact means for recognising the analogy of
elements. Analogous elements give compounds of analogous types, both higher
and lower. If CO2 and SO2 are two gases which closely resemble each other both
in their physical and chemical properties, the reason of this must be looked for
not in an analogy of sulphur and carbon, but in that identity of the type of
combination, RX4, which both oxides assume, and in that influence which a large
mass of oxygen always exerts on the properties of its compounds. In fact, there
is little resemblance between carbon and sulphur, as is seen not only from the
fact that CO2 is the higher form of oxidation, whilst SO2 is able to further oxidise
into SO3, but also from the fact that all the other compounds—for example, SH2
and CH4, SCl2 and CCl4, &c.—are entirely unlike both in type and in chemical
properties. This absence of analogy in carbon and sulphur is especially clearly
seen in the fact that the highest saline oxides are of different composition, CO2
for carbon, and SO3 for sulphur. In Chapter VIII. we considered the limit to
which carbon tends in its compounds, and in a similar manner there is for every
element in its compounds a tendency to attain a certain highest limit RXn. This
view was particularly developed in the middle of the present century by
Frankland in studying the metallo-organic compounds, i.e. those in which X is
wholly or partially a hydrocarbon radicle; for instance, X = CH3 or C2H5 &c. Thus,
for example, antimony, Sb (Chapter XIX.) gives, with chlorine, compounds SbCl3
and SbCl5 and corresponding oxygen compounds Sb2O3 and Sb2O5, whilst under
the action of CH3I, C2H5I, or in general EI (where E is a hydrocarbon radicle of
the paraffin series), upon antimony or its alloy with sodium there are formed
SbE3 (for example, Sb(CH3)3, boiling at about 81°), which, corresponding to the
lower form of combination SbX3, are able to combine further with EI, or Cl2, or
O, and to form compounds of the limiting type SbX5; for example, SbE4Cl
corresponding to NH4Cl with the substitution of nitrogen by antimony, and of
hydrogen by the hydrocarbon radicle. The elements which are most chemically
analogous are characterised by the fact of their giving compounds of similar
form RXn. The halogens which are analogous give both higher and lower
compounds. So also do the metals of the alkalis and of the alkaline earths. And
we saw that this analogy extends to the composition and properties of the
nitrogen and hydrogen compounds of these metals, which is best seen in the
salts. Many such groups of analogous elements have long been known. Thus
there are analogues of oxygen, nitrogen, and carbon, and we shall meet with
many such groups. But an acquaintance with them inevitably leads to the
questions, what is the cause of analogy and what is the relation of one group to
another? If these questions remain unanswered, it is easy to fall into error in the
formation of the groups, because the notions of the degree of analogy will
always be relative, and will not present any accuracy or distinctness Thus lithium
is analogous in some respects to potassium and in others to magnesium;
beryllium is analogous to both aluminium and magnesium. Thallium, as we shall
afterwards see and as was observed on its discovery, has much kinship with lead
and mercury, but some of its properties appertain to lithium and potassium.
Naturally, where it is impossible to make measurements one is reluctantly
obliged to limit oneself to approximate comparisons, founded on apparent signs
which are not distinct and are wanting in exactitude. But in the elements there
is one accurately measurable property, which is subject to no doubt—namely,
that property which is expressed in their atomic weights. Its magnitude indicates
the relative mass of the atom, or, if we avoid the conception of the atom, its
magnitude shows the relation between the masses forming the chemical and
independent individuals or elements. And according to the teaching of all exact
data about the phenomena of nature, the mass of a substance is that property
on which all its remaining properties must be dependent, because they are all
determined by similar conditions or by those forces which act in the weight of a
substance, and this is directly proportional to its mass. Therefore it is most
natural to seek for a dependence between the properties and analogies of the
elements on the one hand and their atomic weights on the other.
This is the fundamental idea which leads to arranging all the elements
according to their atomic weights. A periodic repetition of properties is then
immediately observed in the elements. We are already familiar with examples of
this:—
F =19,Cl =35·5,Br =80,I =127,
Na =23,K =39, Rb=85,Cs =133,
Mg=24,Ca=340, Sr =87, Ba=137.
The essence of the matter is seen in these groups. The halogens have smaller
atomic weights than the alkali metals, and the latter than the metals of the
alkaline earths. Therefore, if all the elements be arranged in the order of their
atomic weights, a periodic repetition of properties is obtained. This is expressed
by the law of periodicity, the properties of the elements, as well as the forms
and properties of their compounds, are in periodic dependence or (expressing
ourselves algebraically) form a periodic function of the atomic weights of the
elements.[8] Table I. of the periodic system of the elements, which is placed at
the very beginning of this book, is designed to illustrate this law. It is arranged
in conformity with the eight types of oxides described in the preceding pages,
and those elements which give the oxides, R2O and consequently salts RX, form
the 1st group; the elements giving R2O2 or RO as their highest grade of
oxidation belong to the 2nd group; those giving R2O3 as their highest oxides
form the 3rd group, and so on; whilst the elements of all the groups which are
nearest in their atomic weights are arranged in series from 1 to 12. The even
and uneven series of the same groups present the same forms and limits, but
differ in their properties, and therefore two contiguous series, one even and the
other uneven—for instance, the 4th and 5th—form a period. Hence the elements
of the 4th, 6th, 8th, 10th, and 12th, or of the 3rd, 5th, 7th, 9th, and 11th, series
form analogues, like the halogens, the alkali metals, &c. The conjunction of two
series, one even and one contiguous uneven series, thus forms one large period.
These periods, beginning with the alkali metals, end with the halogens. The
elements of the first two series have the lowest atomic weights, and in
consequence of this very circumstance, although they bear the general
properties of a group, they still show many peculiar and independent properties.
[9]
Thus fluorine, as we know, differs in many points from the other halogens,
and lithium from the other alkali metals, and so on. These lightest elements may
be termed typical elements. They include—
H.
Li, Be, B, C, N, O, F.
Na, Mg....
In the annexed table all the remaining elements are arranged, not in groups
and series, but according to periods. In order to understand the essence of the
matter, it must be remembered that here the atomic weight gradually increases
along a given line; for instance, in the line commencing with K = 39 and ending
with Br = 80, the intermediate elements have intermediate atomic weights, as is
clearly seen in Table III., where the elements stand in the order of their atomic
weights.
I. II. III.IV. V. VI.VII. I. II. III. IV. V. VI.VII.
Even Series.
MgAl Si P S Cl
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br
Rb Sr Y Zr Nb Mo — RuRhPdAg Cd In Sn Sb Te I
Cs Ba La CeDi? — — — — — — — — — — — —
— — Yb — Ta W — Os Ir Pt Au Hg Tl Pb Bi — —
— — — Th— U
Uneven Series.
The same degree of analogy that we know to exist between potassium,
rubidium, and cæsium; or chlorine, bromine, and iodine; or calcium, strontium,
and barium, also exists between the elements of the other vertical columns.
Thus, for example, zinc, cadmium, and mercury, which are described in the
following chapter, present a very close analogy with magnesium. For a true
comprehension of the matter[10] it is very important to see that all the aspects of
the distribution of the elements according to their atomic weights essentially
express one and the same fundamental dependence—periodic properties.[11] The
following points then must be remarked in it.
1. The composition of the higher oxygen compounds is determined by the
groups: the first group gives R2O, the second R2O2 or RO, the third R2O3, &c.
There are eight types of oxides and therefore eight groups. Two groups give a
period, and the same type of oxide is met with twice in a period. For example, in
the period beginning with potassium, oxides of the composition RO are formed
by calcium and zinc, and of the composition RO3 by molybdenum and tellurium.
The oxides of the even series, of the same type, have stronger basic properties
than the oxides of the uneven series, and the latter as a rule are endowed with
an acid character. Therefore the elements which exclusively give bases, like the
alkali metals, will be found at the commencement of the period, whilst such
purely acid elements as the halogens will be at the end of the period. The
interval will be occupied by intermediate elements, whose character and
properties we shall afterwards describe. It must be observed that the acid
character is chiefly proper to the elements with small atomic weights in the
uneven series, whilst the basic character is exhibited by the heavier elements in
the even series. Hence elements which give acids chiefly predominate among
the lightest (typical) elements, especially in the last groups; whilst the heaviest
elements, even in the last groups (for instance, thallium, uranium) have a basic
character. Thus the basic and acid characters of the higher oxides are
determined (a) by the type of oxide, (b) by the even or uneven series, and (c)
by the atomic weight.[11 bis] The groups are indicated by Roman numerals from I.
to VIII.
2. The hydrogen compounds being volatile or gaseous substances which are
prone to reaction—such as HCl, H2O, H3N, and H4C[12]—are only formed by the
elements of the uneven series and higher groups giving oxides of the forms
R2On, RO3, R2O5, and RO2.
3. If an element gives a hydrogen compound, RXm, it forms an organo-
metallic compound of the same composition, where X = CnH2n+1; that is, X is the
radicle of a saturated hydrocarbon. The elements of the uneven series, which
are incapable of giving hydrogen compounds, and give oxides of the forms RX,
RX2, RX3, also give organo-metallic compounds of this form proper to the higher
oxides. Thus zinc forms the oxide ZnO, salts ZnX2 and zinc ethyl Zn(C2H5)2. The
elements of the even series do not seem to form organo-metallic compounds at
all; at least all efforts for their preparation have as yet been fruitless—for
instance, in the case of titanium, zirconium, or iron.
4. The atomic weights of elements belonging to contiguous periods differ
approximately by 45; for example, K<Rb, Cr<Mo, Br<I. But the elements of the
typical series show much smaller differences. Thus the difference between the
atomic weights of Li, Na, and K, between Ca, Mg, and Be, between Si and C,
between S and O, and between Cl and F, is 16. As a rule, there is a greater
difference between the atomic weights of two elements of one group and
belonging to two neighbouring series (Ti-Si = V-P = Cr-S = Mn-Cl = Nb-As, &c.
= 20); and this difference attains a maximum with the heaviest elements (for
example, Th-Pb = 26, Bi-Ta = 26, Ba-Cd = 25, &c.). Furthermore, the difference
between the atomic weights of the elements of even and uneven series also
increases. In fact, the differences between Na and K, Mg and Ca, Si and Ti, are
less abrupt than those between Pb and Th, Ta and Bi, Cd and Ba, &c. Thus even
in the magnitude of the differences of the atomic weights of analogous elements
there is observable a certain connection with the gradation of their properties.[12
bis]

5. According to the periodic system every element occupies a certain position,

determined by the group (indicated in Roman numerals) and series (Arabic
numerals) in which it occurs. These indicate the atomic weight, the analogues,
properties, and type of the higher oxide, and of the hydrogen and other
compounds—in a word, all the chief quantitative and qualitative features of an
element, although there yet remain a whole series of further details and
peculiarities whose cause should perhaps be looked for in small differences of
the atomic weights. If in a certain group there occur elements, R1, R2, R3, and if
in that series which contains one of these elements, for instance R2, an element
Q2 precedes it and an element T2 succeeds it, then the properties of R2 are
determined by the properties of R1, R3, Q2, and T2. Thus, for instance, the
atomic weight of R2 = ¼(R1 + R3 + Q2 + T2). For example, selenium occurs in
the same group as sulphur, S = 32, and tellurium, Te = 125, and, in the 7th
series As = 75 stands before it and Br = 80 after it. Hence the atomic weight of
selenium should be ¼(32 + 125 + 75 + 80) = 78, which is near to the truth.
Other properties of selenium may also be determined in this manner. For
example, arsenic forms H3As, bromine gives HBr, and it is evident that selenium,
which stands between them, should form H2Se, with properties intermediate
between those of H3As and HBr. Even the physical properties of selenium and its
compounds, not to speak of their composition, being determined by the group in
which it occurs, may be foreseen with a close approach to reality from the
properties of sulphur, tellurium, arsenic, and bromine. In this manner it is
possible to foretell the properties of still unknown elements. For instance in the
position IV, 5—that is, in the IVth group and 5th series—an element is still
wanting. These unknown elements may be named after the preceding known
element of the same group by adding to the first syllable the prefix eka-, which
means one in Sanskrit. The element IV, 5, follows after IV, 3, and this latter
position being occupied by silicon, we call the unknown element ekasilicon and
its symbol Es. The following are the properties which this element should have
on the basis of the known properties of silicon, tin, zinc, and arsenic. Its atomic
weight is nearly 72, higher oxide EsO2, lower oxide EsO, compounds of the
general form EsX4, and chemically unstable lower compounds of the form EsX2.
Es gives volatile organo-metallic compounds—for instance, Es(CH3)4, Es(CH3)3Cl,
and Es(C2H5)4, which boil at about 160°, &c.; also a volatile and liquid chloride,
EsCl4, boiling at about 90° and of specific gravity about 1·9. EsO2 will be the
anhydride of a feeble colloidal acid, metallic Es will be rather easily obtainable
from the oxides and from K2EsF6 by reduction, EsS2 will resemble SnS2 and SiS2,
and will probably be soluble in ammonium sulphide; the specific gravity of Es
will be about 5·5, EsO2 will have a density of about 4·7, &c. Such a prediction of
the properties of ekasilicon was made by me in 1871, on the basis of the
properties of the elements analogous to it: IV, 3, = Si, IV, 7 = Sn, and also II, 5
= Zn and V, 5 = As. And now that this element has been discovered by C.
Winkler, of Freiberg, it has been found that its actual properties entirely
correspond with those which were foretold.[13] In this we see a most important
confirmation of the truth of the periodic law. This element is now called
germanium, Ge (see Chapter XVIII.). It is not the only one that has been
predicted by the periodic law.[14] We shall see in describing the elements of the
third group that properties were foretold of an element ekaaluminium, III, 5, El
= 68, and were afterwards verified when the metal termed ‘gallium’ was
discovered by De Boisbaudran. So also the properties of scandium corresponded
with those predicted for ekaboron, according to Nilson.[15]
6. As a true law of nature is one to which there are no exceptions, the
periodic dependence of the properties on the atomic weights of the elements
gives a new means for determining by the equivalent the atomic weight or
atomicity of imperfectly investigated but known elements, for which no other
means could as yet be applied for determining the true atomic weight. At the
time (1869) when the periodic law was first proposed there were several such
elements. It thus became possible to learn their true atomic weights, and these
were verified by later researches. Among the elements thus concerned were
indium, uranium, cerium, yttrium, and others.
7. The periodic variability of the properties of the elements in dependence on
their masses presents a distinction from other kinds of periodic dependence (as,
for example, the sines of angles vary periodically and successively with the
growth of the angles, or the temperature of the atmosphere with the course of
time), in that the weights of the atoms do not increase gradually, but by leaps;
that is, according to Dalton's law of multiple proportions, there not only are not,
but there cannot be, any transitive or intermediate elements between two
neighbouring ones (for example, between K = 39 and Ca = 40, or Al = 27 and
Si = 28, or C = 12 and N = 14, &c.) As in a molecule of a hydrogen compound
there may be either one, as in HF, or two, as in H2O, or three, as in NH3, &c.,
atoms of hydrogen; but as there cannot be molecules containing 2½ atoms of
hydrogen to one atom of another element, so there cannot be any element
intermediate between N and O, with an atomic weight greater than 14 or less
than 16, or between K and Ca. Hence the periodic dependence of the elements
cannot be expressed by any algebraical continuous function in the same way
that it is possible, for instance, to express the variation of the temperature
during the course of a day or year.
8. The essence of the notions giving rise to the periodic law consists in a
general physico-mechanical principle which recognises the correlation,
transmutability, and equivalence of the forces of nature. Gravitation, attraction
at small distances, and many other phenomena are in direct dependence on the
mass of matter. It might therefore have been expected that chemical forces
would also depend on mass. A dependence is in fact shown, the properties of
elements and compounds being determined by the masses of the atoms of
which they are formed. The weight of a molecule, or its mass, determines, as
we have seen, (Chapter VII. and elsewhere) many of its properties
independently of its composition. Thus carbonic oxide, CO, and nitrogen, N2, are
two gases having the same molecular weight, and many of their properties
(density, liquefaction, specific heat, &c.) are similar or nearly similar. The
differences dependent on the nature of a substance play another part, and form
magnitudes of another order. But the properties of atoms are mainly determined
by their mass or weight, and are in dependence upon it. Only in this case there
is a peculiarity in the dependence of the properties on the mass, for this
dependence is determined by a periodic law. As the mass increases the
properties vary, at first successively and regularly, and then return to their
original magnitude and recommence a fresh period of variation like the first.
Nevertheless here as in other cases a small variation of the mass of the atom
generally leads to a small variation of properties, and determines differences of
a second order. The atomic weights of cobalt and nickel, of rhodium, ruthenium,
and palladium, and of osmium, iridium, and platinum, are very close to each
other, and their properties are also very much alike—the differences are not very
perceptible. And if the properties of atoms are a function of their weight, many
ideas which have more or less rooted themselves in chemistry must suffer
change and be developed and worked out in the sense of this deduction.
Although at first sight it appears that the chemical elements are perfectly
independent and individual, instead of this idea of the nature of the elements,
the notion of the dependence of their properties upon their mass must now be
established; that is to say, the subjection of the individuality of the elements to a
common higher principle which evinces itself in gravity and in all physico-
chemical phenomena. Many chemical deductions then acquire a new sense and
significance, and a regularity is observed where it would otherwise escape
attention. This is more particularly apparent in the physical properties, to the
consideration of which we shall afterwards turn, and we will now point out that
Gustavson first (Chapter X., Note 28) and subsequently Potilitzin (Chapter XI.,
Note 66) demonstrated the direct dependence of the reactive power on the
atomic weight and that fundamental property which is expressed in the forms of
their compounds, whilst in a number of other cases the purely chemical relations
of elements proved to be in connection with their periodic properties. As a case
in point, it may be mentioned that Carnelley remarked a dependence of the
decomposability of the hydrates on the position of the elements in the periodic
system; whilst L. Meyer, Willgerodt, and others established a connection
between the atomic weight or the position of the elements in the periodic
system and their property of serving as media in the transference of the
halogens to the hydrocarbons.[16] Bailey pointed out a periodicity in the stability
(under the action of heat) of the oxides, namely: (a) in the even series (for
instance, CrO3, MoO3, WO3, and UO3) the higher oxides of a given group
decompose with greater ease the smaller the atomic weight, while in the uneven
series (for example, CO2, GeO2, SnO2, and PbO2) the contrary is the case; and
(b) the stability of the higher saline oxides in the even series (as in the fourth
series from K2O to Mn2O7) decreases in passing from the lower to the higher
groups, while in the uneven series it increases from the Ist to the IVth group,
and then falls from the IVth to the VIIth; for instance, in the series Ag2O, CdO,
In2O3, SnO2, and then SnO2, Sb2O5, TeO3, I2O7. K. Winkler looked for and
actually found (1890) a dependence between the reducibility of the metals by
magnesium and their position in the periodic system of the elements. The
greater the attention paid to this field the more often is a distinct connection
found between the variation of purely chemical properties of analogous
substances and the variation of the atomic weights of the constituent elements
and their position in the periodic system. Besides, since the periodic system has
become more firmly established, many facts have been gathered, showing that
there are many similarities between Sn and Pb, B and Al, Cd and Hg, &c., which
had not been previously observed, although foreseen in some cases, and a
consequence of the periodic law. Keeping our attention in the same direction,
we see that the most widely distributed elements in nature are those with small
atomic weights, whilst in organisms the lightest elements exclusively
predominate (hydrogen, carbon, nitrogen, oxygen), whose small mass facilitates
those transformations which are proper to organisms. Poluta (of Kharkoff), C. C.
Botkin, Blake, Brenton, and others even discovered a correlation between the
physiological action of salts and other reagents on organisms and the positions
occupied in the periodic system by the metals contained in them.[17]
As, from the necessity of the case, the physical properties must be in
dependence on the composition of a substance, i.e. on the quality and quantity
of the elements forming it, so for them also a dependence on the atomic weight
of the component elements must be expected, and consequently also on their
periodic distribution. We shall meet with repeated proofs of this in the further
exposition of our treatise, and for the present will content ourselves with citing
the discovery by Carnelley in 1879 of the dependence of the magnetic properties
of the elements on the position occupied by them in the periodic system.
Carnelley showed that all the elements of the even series (beginning with
lithium, potassium, rubidium, cæsium) belong to the number of magnetic
(paramagnetic) substances; for example, according to Faraday and others,[17 bis]
C, N, O, K, Ti, Cr, Mn, Fe, Co, Ni, Ce, are magnetic; and the elements of the
uneven series are diamagnetic, H, Na, Si, P, S, Cl, Cu, Zn, As, Se, Br, Ag, Cd, Sn,
Sb, I, Au, Hg, Tl, Pb, Bi.
Carnelley also showed that the melting-point of elements varies periodically,
as is seen by the figures in Table III. (nineteenth column),[18] where all the most
trustworthy data are collected, and predominance is given to those having
maximum and minimum values.[19]
There is no doubt that many other physical properties will, when further
studied, also prove to be in periodic dependence on the atomic weights,[19 bis]
but at present only a few are known with any completeness, and we will only
refer to the one which is the most easily and frequently determined—namely,
the specific gravity in a solid and liquid state, the more especially as its
connection with the chemical properties and relations of substances is shown at
every step. Thus, for instance, of all the metals those of the alkalis, and of all
the non-metals the halogens, are the most energetic in their reactions, and they
have the lowest specific gravity among the adjacent elements, as is seen in
Table III., column 17. Such are sodium, potassium, rubidium, cæsium among
the metals, and chlorine, bromine, and iodine among the non-metals; and as
such less energetic metals as iridium, platinum, and gold (and even charcoal or
the diamond) have the highest specific gravity among the elements near to
them in atomic weight; therefore the degree of the condensation of matter
evidently influences the course of the transformations proper to a substance,
and furthermore this dependence on the atomic weight, although very complex,
is of a clearly periodic character. In order to account for this to some extent, it
may be imagined that the lightest elements are porous, and, like a sponge, are
easily penetrated by other substances, whilst the heavier elements are more
compressed, and give way with difficulty to the insertion of other elements.
These relations are best understood when, instead of the specific gravities
referring to a unit of volume,[20] the atomic volumes of the elements—that is,
the quotient A/d of the atomic weight A by the specific gravity d—are taken for
comparison. As, according to the entire sense of the atomic theory, the actual
matter of a substance does not fill up its whole cubical contents, but is
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