Assignment 60 MOLAR CONCENTRATION (AND OTHERS)

A solution is a homogeneous mixture of one of more solutes with a solvent. The solvent is generally the major component of the mixture, but this is not a necessary criterion. Solutions may exist in any of the states of matter; however, the principal kind of solution to be considered here is in the liquid state. Furthermore, most of the liquid solutions of interest will be aqueous (water) solutions in which the solvent is water, and the solutes may be gases, liquids, or solids. The concentration of a solution is a measure of the relative amount of the solute present in the solution. We may speak of the concentration in a purely qualitative manner as concentrated or dilute, but these terms have little significance for calculations and they depend on the nature of the solute. For example, concentrated sulfuric acid contains about 175 grams of H2SO4 in each 100 mL of solution, while concentrated AgCl (a relatively insoluble solid) contains about -3 0.0015 grams (or 1.5 x 10 g) of dissolved AgCl in each 100 mL of solution. For purposes of calculation, a more quantitative measure of the relative amount of solute present in the solution is required. The most significant measure molar concentration or molarity is emphasized in this assignment. Some of the other quantitative measures will be included as well.

A)

Molarity.

From the chemical point of view, great importance is associated with a measure of concentration which involves the chemical units of moles. The molar concentration is the expression most frequently used, and it is defined as the number of moles of solute per liter of solution. The abbreviation used for molar concentration is M , and the units are moles/liter, where the "liter" refers to a liter of solution. moles solute 1, for molar concentration, M, serves as a useful conversion factor. It may be inverted The definition, liter solution (including the value) whenever the dimensions need to be inverted for a calculation. mol KOH 1 liter soln 6 Example: may be inverted to read liter soln 6 mol KOH

Through consideration of the dimensions, it is possible quantities. For example: grams solute molecular weight, g moles solute mol molar conc . = = liter solution liters soln .

to calculate molar concentration from a wide variety of

= grams solute x mol solute liters soln . grams solute

Also, as a consequence of the dimensions, molar concentration can be used to compute other quantities: moles of solute = molar conc . x liters solution
mol mol = x(L L

grams of solute = molar conc . x liters soln . x ( molecular weight, g/mol )

mol g g = x ( L )x L mol

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liters of solution =

moles solute grams solute = ( molec . wt . solute, g/mol ) molar conc . (mol) = mol L

1 ( molar conc ., mol/L )

liters soln . =

( g ) x mol

1 x = g mol L

( g ) x mol x

L g mol

Note especially that volume of solution x molar concentration = moles ; this relation provides a very convenient means of measuring out (or obtaining) a quantity of moles:

( L soln . ) x mol solute

L soln .

= mol solute

Previous computations of moles (in earlier problem sets) have made use of mol gas = mol gas the GMV: LSTP x LSTP gas the MW: the Avogadro number: mol substance g substance x g substance mol molec . x = mol ; molec . = mol substance etc .

Examples of calculations that involve molarity:

1)

Calculations of the molarity of a solution:

a) What is the molarity if there is 0.57 mole of solute in 750 mL of solution? Moles solute 0.57 mol solute mol = = 0.76 = 0.76 M liter soln 0.750 L soln . L

b) What is M if 57.3 g of HCl (MW = 36.5) is dissolved in 125 mL of solution? 1 mol HCl Moles HCl 1 mol HCl = ( 57.3 g HCl ) x 36.5 g HCl x 0.125 L soln = 12.6 L soln = 12.6 M HCl liter soln

The grams are converted to moles, then divided by liters of the solution formed (note that liters are placed in the denominator in the set-up), in order to obtain units of molarity.
What is M if 11.2 liters(STP) of NH3 gas are dissolved in water to form 2.50 102 milliliters of solution? 1 mol NH3 Moles NH3 1 x = ( 11.2 LSTP NH3 ) x = 2.00 M NH3 22.4 Liters soln 0.250 L soln LSTP NH3 c)

The liters(STP) are converted to moles, which then are divided by the volume of solution formed, in order to obtain the desired units.

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2)

Calculations of moles of solute: a)

How many moles of solute are required to prepare 3.5 liters of 0.85 M KF (potassium fluoride) solution? 0.85 mol KF ? moles KF = ( 3.5 L soln ) x = 3.0 mol KF needed as solute 1 L soln How many moles of methanol, CH3OH, are present in 140 mL of a 0.25 M solution of methanol in water? 0.25 mol CH3 OH ? moles CH3 OH = ( 0.140 L soln ) x = 0.035 mol CH 3 OH 1 L soln b)

Note that the word, of, always implies multiplication.

3)

Calculation of mass of solute: a)

How many grams of solute occur in 4.05 liters of 1.25 M H2SO4 (MW = 98.1)? 1.25 mol H 2 SO 4 98.1 g H 2 SO4 = 495 g H 2 SO 4 ? grams H 2 SO4 = ( 4.05 L soln ) x x 1 L soln 1 mol H 2 SO 4 How many grams of NaCl (MW = 58.5) are required to prepare 75 mL of 2.5 M solution? mol NaCl g NaCl ? grams NaCl = ( 0.075 L soln ) x 2.5 x 58.5 = 11 g NaCl L soln mol NaCl b)

4)

Calculation of solution volumes: a)

What volume of 6.0 M solution is required to furnish or contain 2.0 moles of solute? 1 L soln ? liters soln = ( 2.0 mol solute ) x = 0.33 L soln 6.0 mol solute b) What volume of 0.550 M solution of H2SO4 (MW = 98.1) contains 28.3 g of H2SO4?

Starting with the "grams" data, convert grams H2SO4 to moles H2SO4 by means of the MW; then convert moles H2SO4 to liters of solution by means of the molar concentration. The single-line set-up is: ? liters soln =

( 28.3 g H 2 SO 4 ) x 1 mol H 2 SO4 x

1 L soln = 0.520 L soln 98.1 g H 2 SO 4 0.550 mol H 2 SO4

An alternate, equally correct sequence is possible by starting instead with the "molarity" data. But this data must be inverted so as to position volume in the numerator,

thus:

1 L soln 0.550 mol H 2 SO 4

Now by use of the MW, also inverted, convert the moles of H2SO4 into grams of H2SO4 ; then multiply by the "grams" data to obtain the desired final dimension: 1 L soln ? liters soln = 0.550 mol H 2 SO4 1 mol H 2 SO 4 x x ( 28.3 g H 2 SO 4 ) = 0.520 L soln 98.1 g H 2 SO 4 01-111-60-3

5)

Calculations involving gases as well as solutions: What volume(STP) of HCl gas should be dissolved in water to make 0.200 L of 0.15 M HCl solution?

Recall that the word, of, signifies multiplication. First, determine the moles of HCl needed; then find the liters(STP) by use of the GMV conversion. 0.15 mol HCl 22.4 LSTP gas ? LSTP gas = ( 0.200 L soln ) x x = 0.67 LSTP of HCl gas 1 L soln 1 mol HCl
OR

an alternative set-up may begin with the known GMV relationship, with subsequent multiplications to eliminate unwanted dimensions:

22.4 LSTP gas 0.15 mol HCl ? LSTP gas = x x ( 0.200 L soln 1 mol HCl 1 L soln

) = 0.67 LSTP of HCl gas

Note the crucial distinction that must be drawn between the LSTP of gas and the L of solution, in order to answer question (5) correctly.

Frequently, the concentration of a particular ion in the solution is used. For these calculations, the molecular weight of the ion is equal to the sum of atomic weights in the formula of the ion.
Examples: 1) What is M of NH4+ (ammonium ion) in a 3.0 M solution of (NH4)2SO4 ?

A 3.0 M solution of (NH4)2SO4 contains 3.0 moles of (NH4)2SO4 per liter of solution. Therefore,
+

3 mol ( NH 4 )2 SO 4 1 L soln

There are 2 moles of NH4 per 1 mole of (NH4)2SO4.

Therefore,

2 mol NH + 4 1 mol ( NH ) SO 4 2 4

The single-line answer, therefore, is: Moles NH + 3.0 mol ( NH 4 )2 SO 4 4 = Liter soln 1 L soln
+ 2 mol NH + 4 = 6.0 mol NH 4 or 6.0 M NH + x 4 1 mol ( L NH 4 ) 2 SO 4

2)

What is M of Cl (chloride ion) in a solution containing 1.11 grams of CaCl2 (MW = 111) in exactly 300 milliliters of solution?

The desired dimension is mol Cl/L soln. Convert the known grams of CaCl2 to moles of CaCl2 (by means of MW of CaCl2), but invert the MW so as to 111 g CaCl2 . position the dimensions appropriately: 1 mol CaCl2

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Then, to convert the moles of CaCl2 to moles of Cl! ion, use a mol/mol relationship obtained from the 2 mol Cl- 2+ composition of the substance, Ca Cl2 : 1 mol CaCl . 2 Finally, in order to obtain the desired molar dimensions, divide the moles of Cl (i.e., the entire sequence of factors thus far) by the known volume, 0.300 L . The individual steps (described above) would be these: ( 1.11 g CaCl2 ) x 1 mol CaCl2 = 0.0100 mol CaCl2 111 g CaCl2 2 mol Cl- 0.100 mol CaCl2 x 1 mol CaCl = 0.0200 mol Cl 2 0.200 mol Clmol Cl= 0.0667 or 0.0667 M Cl( 0.300 L soln ) L soln

The overall, complete set-up requires only a single numerical calculation at the end:
( 1.11 g CaCl2 ) x 1 mol CaCl2 x 2 mol Cl- 111 g CaCl2 1 mol CaCl 2 ( 0.300 L soln )

Moles Cl= Liter soln

OR

= 0.667

mol Clor 0.667 M ClL soln

even more simple for calculation, the division may be set-up by inversion and multiplying:

1 mol CaCl 2 2 mol Cl- Moles Cl x x = ( 1.11 g CaCl2 ) x 111 g Liter soln CaCl2 1 mol CaCl2

1 ( 0.300 L soln

= 0.667

mol ClL soln

3)

How many moles of NO3 are present in 6.0 x 102 mL of 1.5 M Cd2+(NO3)2 ?

Multiply

( 0.60 L ) x

1.5 mol Cd( NO3 ) 2 2 to obtain moles of Cd(NO3)2 . 1L

2 mol NO3 Then convert to moles NO3 by means of the formula relationship, 1 mol Cd( NO ) 3 2

Arranged as a single-line set-up:

1.5 mol Cd( NO3 )2 2 mol NO3 = 1.8 mol NO3 x ? moles NO- = ( 0.60 L ) x 3 1 mol Cd( 1L NO3 ) 2

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4)

Grams Na+ in 2.5 liters of 0.80 M Na2SO4 ?

+ Then convert to moles of Na ion; 2 mol Na + provides the mol/mol conversion factor: 1 mol Na SO . 2 4

First, seek the moles of Na2SO4 solute.

the formula of Na2SO4

+ + Finally, convert moles of Na to grams of Na , by use of the AW of sodium (ignore the negligible mass effect of + the electron missing from Na ion).

The complete set-up is: ? grams Na + =

( 2.5 L ) x 0.80 mol Na 2 SO 4 x

1L

2 mol Na + 23 g Na + x = 92 g Na + 1 mol Na 2 SO 4 1 mol Na +

THE DILUTING OR CONCENTRATING OF SOLUTIONS.

An important type of problem for chemists involves changing the concentration of a solution, either by diluting with more solvent, or by concentrating a solution through removal of solvent (as by boiling or distillation). A related aspect is the preparation of a solution of required concentration from another solution of a different concentration. The essential feature of problems of these types is that the number of moles of solute is not changed while the volume of the solution becomes changed (since only solvent is being added or removed). mol As a consequence of the definition of molarity, M: moles solute = liters x liter then, with moles of solute remaining the same, mol mol liters x of the original solution = moles solute = liters x of the new solution liter liter

Examples: 1) What is the molarity of a solution formed by diluting 58 mL of 3.6 M KBr solution to a volume of 2.5 liters by the addition of more solvent?

2.5 L (new solution) 0.058 L (original solution) 3.6 mol KBr ( 0.058 L(orig.) ) x (orig .) = ( 2.5 L(new) ) x ( New Molarity ) 1L By rearrangement of factors in the equation, 1 3.6 mol KBr = 0.084 mol KBr or 0.084 M KBr New Molarity = ( 0.058 L ) x x 2.5 L(new) 1L L (Note that the array of dimensions here does give the units of molarity, moles KBr / L , for the new solution.)

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2) 725 mL of 0.350 M LiCl solution is concentrated to exactly 500 mL by boiling off some solvent. What is the final concentration?

0.725 L (orig.)

0.500 L (new)

( 0.725 L(orig.) ) x 0.350 mol LiCl (orig .) = ( 0.500 L(new) ) x ( New Molarity )
1L
Moles LiCl 1 mol LiCl 0.350 mol LiCl (new) = (0.725 L(orig .) ) x (orig .) x (0.500 L(new) ) = 0.508 L (new) 1L Liters soln Note that the final calculation has this overall design: New Molarity wanted = ( moles of solute present ) x 1 ( Liters(new)

3)

What volume of 2.0 M NaI solution must be taken to prepare 750 ml of 0.50 M NaI solution?

2.0 M NaI (orig.) 0.50 M NaI (final) 2.0 mol NaI 0.50 mol NaI ( Orig . Liters ) x (final) (orig .) = ( 0.75 L(final) ) x L 1L With rearrangement of factors, the final set-up is: 1L 0.50 mol NaI (orig .) = 0.19 L (orig .) (final) x Orig . Liters = ( 0.75 L(final) ) x 2.0 mol NaI 1L Note that the final calculation has this overall design: liters soln (orig .) Orig. Liters needed = ( moles of solute needed ) x moles solute Observe that the factor at right is the original solution's molarity in inverted form.

4)

What volume of 0.75 M HF solution may be prepared from 1.5 liters of 3.5 M HF solution?

0.75 M HF (new) from 3.5 M HF (orig.) ( New Liters ) x 0.75 mol HF (new) = ( 1.5 L(orig .) ) x 3.5 mol HF (orig .) 1L 1L In rearranged form: 1L 3.5 mol HF (new) = 7.0 L (new soln) (orig .) x New Liters = ( 1.5 L(orig .) ) x 0.75 mol HF 1L

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THE MIXING OF TWO OR MORE SOLUTIONS.

Another important type of problem involving concentration is that of changing both the amount of solute and the total volume of the solution, as illustrated by mixing two or more solutions. At present, we will mix solutions which do not chemically react; however, in later assignments, we will mix solutions (by a process called titration) in which the amounts of the solutes will change due to chemical reactions that occur when solutions are mixed. (In the problems below, when solutions are mixed, we assume the volumes are additive. This is a reasonable approximation where dilute solutions are being mixed. However, especially in cases where concentrations are large, actual experiments may reveal a deviation from the expected total volume, owing to a lack of strict additivity of volume when solutions are mixed.)
Examples: 1) What is the final concentration of the solutes (H2SO4 and NaHSO4) in a solution formed by combining 100.0 mL of 3.0 M H2SO4 and 100.0 mL of 1.5 M NaHSO4 ? (The two solutes do not react with one another in this new solution.)

Each solute should be calculated individually. The desired dimensions for each final molarity are: (moles of solute)/(total liters of solution) . Therefore, in each set-up, determine the number of moles of the solute, and divide by the total volume. Total Final Liters = 0.1000 L + 0.1000 L = 0.2000 L (assuming solution volumes are additive)

mol H 2 SO 4 1 Moles H 2 SO 4 3.0 mol H 2 SO 4 (orig .) x (final) = (0.1000 L(orig .) ) x (0.2000 L(final)) = 1.5 L 1L L 1 mol NaHSO 4 Mol NaHSO 4 1.5 mol NaHSO 4 (orig .) x (final) = (0.1000 L(orig .) ) x (0.2000 L(final)) = 0.75 L L L

2)

What is the molarity of NO3 in a solution prepared by mixing 75.5 mL of 0.86 M K+NO3 and 143.72 mL of 1.35 M Mg++(NO3)2 ?

The answer can be expressed in single-line fashion if you write small enough! but will be shown here as a stepwise answer. To solve the problem, one has to determine the total number of moles of NO3 from each source and then divide that total by the total number of liters of final solution. Total Final Liters = 0.0755 L + 0.14372 L = 0.2192 L total (assuming volume additivity)

(Remember to observe sig.figs. carefully whenever quantities are being summed.)

Also note the various mol/mol conversion factors needed to obtain moles of NO3! ion: 0.86 mol KNO3 1 mol NO- 3 Moles NO3 in KNO3 = ( 0.0755 L ) x x = 0.065 mol NO3 1L 1 mol KNO3
1.35 mol Mg( NO3 )2 2 mol NO3 = 0.388 mol NO3 Moles NO3 in Mg( NO3 )2 = ( 0.14372 L ) 1 mol Mg( 1L NO3 )2 Total moles NO3 = 0.065 mol NO3 + 0.388 mol NO3 = 0.453 mol NO3

The final molarity of NO3! is the total moles NO3! divided by total liters:
Total Molarity NO3 = (0.065 mol NO3 + 0.388 mol NO3) = ( 0.453 mol NO-3 ) = 2.07 M NO-

( 0.0755 L

+ 0.14372 L

( 0.2192 L total )

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CALCULATIONS INVOLVING CHEMICAL REACTIONS.

In many laboratory procedures, reactions occur that involve reagents dissolved in solutions. In such cases, the quantity of the reagent is determined by measurement of the volume of solution used, in which the reagent is the solute. Recall that (L x mol/L ) equals moles of solute.
Example: If 45.0 mL of 1.25 M AgNO3 solution is added to a solution containing excess CrO42, how many grams of solid Ag2CrO4 are produced? The chemical reaction is: Ag2CrO4 (s) 2 Ag+ + CrO42

First, from the given data (volume and molarity of reagent solution), find the moles of AgNO3 solute being added, then moles of Ag+ (by means of the mol/mol conversion factor deduced from the AgNO3 formula), then moles of Ag2CrO4 formed in the reaction (the balanced equation provides the necessary mol/mol conversion factor), then finally the grams of Ag2CrO4 product formed (determined by means of the MW of the compound). Construction of a single-line set-up, adopting the above sequence of conversions, gives: 1.25 mol AgNO3 1 mol Ag+ 1 mol Ag2 CrO 4 332 g Moles Ag 2 CrO 4 = ( 0.0450 L ) 1 mol AgNO + 1 mol Ag CrO 4 1L 2 mol Ag 3 2 = 0.045 x 1.25 x 332 g Ag2 CrO 4 = 9.35 g Ag 2 CrO 4 2

Constructing single-line set-ups is highly efficient for presenting the entire detail of a calculation in a minimum of time and space, and for revealing all the crucial information needed for expressing the final answer with correct sig.figs. Even so, some problems can require quite a lengthy set-up, especially when several changes of formula must occur (as in the problem above) where a series of mol/mol conversions can quickly exhaust the space of a "single line." Formulas must be shown, for any changes of formula are crucial to the solving of chemical problems. Repetitive writing of mol, however, may be simplified. In set-ups of chemical problems, it is customary to adopt the following convention of notation:
Whenever a formula is written as a dimension without other units being specified, the mol dimension is automatically implied as well. 1 mol Ag2 CrO 4 1 Ag2 CrO 4 may simplified to Thus, a mol/mol conversion factor such as 2 mol Ag+ 2 Ag+ . Accordingly, the previous set-up may be stated more briefly as follows: 1.25 mol AgNO3 1 Ag + 1 Ag2 CrO 4 332 g Grams Ag2 CrO 4 = (0.045 L ) 1 AgNO + 1 mol Ag CrO = 9.35 g Ag2 CrO 4 1L 2 Ag 4 3 2

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B)

Formality or formal concentration:

In some chemistry texts and laboratory manuals, the symbol F is used to represent the formal concentration. In these sources, F is defined as the number of formula weights of solute per liter of solution. The distinction between F (formality) and M (molarity) is a fine one which requires further chemical knowledge it depends either on the nature of the solute (whether ionic or molecular in the pure state) or on the fact that particles in solution often differ in subtle ways from the non-dissolved particles. For the purposes of this course, the units F and M may be used interchangeably; both represent the units, moles of solute/liter of solution, and no distinction is made between a molecular weight and a formula weight. In the problem assignments, M will be used exclusively.

C)

Molality or molal concentration: (Note the fifth letter of the word!)

Molality is defined as the number of moles of solute per kg of solvent (note that the denominator pertains only to the solvent's mass, rather than that of the entire solution).

In contrast, molarity is defined as the number of moles of solute per liter of solution (the volume of solvent plus solute).
Molal concentration is sometimes symbolized by a small letter, m , in contrast to molar concentration which is symbolized by a capital letter, M .

Thus, 0.07 m NaCl means 0.07 mol NaCl/kg solvent and not 0.07 mol NaCl/liter solution and not 0.07 mol NaCl. Molality is used in calculations involving the freezing point depression or boiling point elevation of solutions, but examples will not be presented in this Problem Manual.

D)

Grams solute per 100 grams solvent:

The solubility of a solute is defined as the equilibrium limit of amount of solute that dissolves in solution at a definite temperature. Solubility values are listed in handbook tables, often with the dimensions: grams of dissolved solute per 100 grams of solvent at a stated temperature. The only practical use made of this style of concentration measurement is for these solubilities.
Examples: 1) It is found that the equilibrium amount of a certain solute which can be dissolved at 25oC is 5.60 g in 25.0 g of solvent; what is the solubility in g/100 g solvent? 5.60 g solute 100 g solvent Solubility at 25 C = x 25.0 g solvent (100 g solvent)

g solute 22.4 g solute 5.60 x 100 = = (100 g solvent) 25.0 (100 g solvent)

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2)

A solution, containing 15.8 g of solute dissolved at equilibrium, weighs 82.3 g; what is the solubility? 15.8 solute 100 g solvent Solubility = x ( 82.3 g solution - 15.8 g solute ) (100 g solvent)

15.8 g solute 100 g solvent x 66.5 g solvent (100 g solvent) g solute (100 g solvent)

= 23.8

3)

How many grams of solute are present at equilibrium in 87.0 g of solvent if the solubility is 12.4 g/(100 g solvent)? 12.4 g solute Grams solute = 87.0 g solvent x (100 g solvent)

= 10.8 g solute

E)

Mole Fraction (and Mole Percent):

In some chemical applications it is convenient to use a concentration unit based completely on moles. One then defines the following: moles of the component Mole Fraction of a component = total number of moles of all components (Also, Mole Percent of a component = Mole Fraction x 100)

The symbol, X, is most frequently used for mole fraction, and a subscript is used to designate the component: X HCl = mole fraction of HCl in a sample . Also, the symbol, n, is used for number of moles, with a subscript to designate the component: n HCl = moles of HCl in a sample . One useful feature of the mole fraction is that the sum of the mole fractions of each component in a sample must equal exactly 1. (Similarly, mole percents must sum to 100%.)
Examples: 1) A solution contains 1.3 moles of HCl and 16.5 moles of water. What are the mole fractions of the components?
n

HCl

=
n

1.3 mol HCl;

n

H2O =

16.5 mol H2O; total =

17.8 mol total

XHCl

= HCl / total = 1.3 mol HCl / 17.8 mol total = 0.073

X H2O = 1.000 0.073 = 0.927 or = H2O / total = 16.5 mol H2O /17.8 mol total = 0.927
n n

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2) What are the mole fractions in a sample which contains 48 g of NaOH, 11.7 g of NaCl, and 250.0 mL of H2O? 1 mol NaOH nNaOH = 48 g NaOH x = 1.2 mol NaOH 40 g NaOH

nNaCl = 11.7 g NaCl x

1 mol NaCl = 0.200 mol NaCl 58.5 g NaCl g 1 mol H 2 O x = 13.87 mol H 2 O mL 18.02 g H 2 O

n H 2 O = 250.0 mL H 2 O x 1.000

n total = (1.2 + 0.200 + 13.87) mol = 15.3 mol total

XNaOH =

1.2 mol NaOH = 0.078 15.3 mol total

XNaCl =

1.2 mol NaCl = 0.0131 15.3 mol total 13.87 mol H 2 O = 0.907 15.3 mol total or 1.00 when rounded (as expected)

X H2 O =

Xtotal = 0.078 + 0.0131 + 0.907 = 0.998

An overall single-line set-up of the calculation for XNaOH above (i.e., the mole fraction of NaOH in the solution) might be written this way:
1 mol NaOH 48 g x 40 g ( 1.2 mol NaOH ) = 1 NaOH 1 NaCl g 1 O (1.2 + 0.200 + 13.87 )mol 48 g x + 11.7 g x + 250.0 mL x 1.000 x H2 40 g 58.5 g mL 18.02 g

(Recall that whenever a written formula is accompanied by no other dimension, in a set-up for a calculation, it is presumed that a mole dimension is intended. For a cumbersome array of terms and factors, such as this calculation requires, it is often convenient to omit a reiterative use of the "mol" unit. The formulas of the pertinent substances, however, need to be specified throughout.)

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