There were a number of good solutions to this problem and I have picked several to illustrate the different approaches adopted.

First Fred and Matt from Albion Heights sent in a solution, which I rather liked. They have not explained why they did not try 1/3 as the first fraction or give full reasoning for why they knew they had a largest value, but the argument as far as it goes is a good one. I have added some examples below to illustrate what they said in a little more detail. I have included a solution based on the one from Tom or STRS, which was similar to that of Curt from Reigate School . Andrei, of Tudor Vianu College, also looked for solutions using a spreadsheet and sent in a program in C++ to search for soultions. I have included this below.

Well done to all of you.

First Fred and Matt's approach to get us started::

To crack the puzzle we tried using algebra but it did not work so we took this problem from a different approach.
Our answer to this puzzle is p=2 q=3 and r=7 and this would end up like this 1/2+1/3+1/7=41/42 .
We also tried a number of other combination but none of them was as close as this one and this is how we were thinking:
If one of the fractions is 1/2 then this puzzle would be slightly easier. Then we had to try the other two numbers. Of couse the total of the other two should be less than 1 otherwise this puzzle would equal or be more than one so the second number has to be 1/3 1/4 1/5 .... and so on.
If you take1/3 for one of the fractions, the last number has to be 1/7 for the closest result (the bigger the denominator is the smaller the number is).
If you take 1/4 then the last fraction would be 1/3 for the closest result.
Then we figure out when we use 1/2 then all we have to do is find two other numbers that add up to less than 1/2 and we know that 1/3 and 1/6 add to 1/2 so instead of 6 we used 7 and this made the answer smaller because the denonminator is bigger.

To make a fraction as large as possible you need to make the denominator as small as possible. The smallest a denominator can be is 2. All the denominators cannot be 2 because:
1
2
+ 1
2
+ 1
2
= 3
2
which is > 1
The next we can try then is
1
2
+ 1
3
+ 1
2
= 4
3
which is > 1
Then try the next largest value, which is:
1
2
+ 1
3
+ 1
3
= 7
6
which is > 1
This is getting closer to 1 but is still greater than 1

Try denominators of 2, 3 and 4 giving:
1
2
+ 1
3
+ 1
4
= 13
12
which is > 1
Continuing in this way, the first set of fractions that give a total less than 1 and with the smallest possible denominators (and largest sum) is: I will use the notation (p,q,r) when referring to set of values for the variables.

First I will eliminate the '3rd dimension' to this problem by proving that p = 2. To simplify the explanation I will always have p as the lowest variable, this is OK as p q and r are interchangeable without affecting the sum.

If p = 3, q > = 3 and r > = 3 as p is the lowest variable. The greatest sum in this case is:

(3,3,4) sum = 11/12 as this is the minimum value each variable can take, therefore maximising the reciprocals. (3,3,3) gives 1 exactly which is not permissible as the sum must be < 1.

For p > = 4, the greatest sum will be given by p, q and r all being equal ie (p,p,p), as this minimises them (they cannot be higher than p as that is the lowest). The sum will be:
3 * ( 1 / p ) = 3 / p
As p > = 4, this cannot exceed 3/4. Now consider the case (2,3,7). The sum here is 41/42, which is greater than the maximum established for p = 3 and p ³ 4. As p is a positive integer, and p = 0, p = 1 both invalidate the condition that the sum must be lower than 1, it is proven that p = 2.

The solution is (2,3,7), or if there is a one greater still it too must occur where p = 2.

Now I will prove that (2,3,7) in fact gives the maximum.

It is proven that p = 2, therefore:
1/2 + 1/q + 1/r
<
1
1/q + 1/r
<
1/2
q + r
<
qr/2
2q + 2r - qr
<
0
qr - 2q - 2r
>
0
q(r - 2) - 2r
>
0
q(r - 2)
>
2r
q
>
(2r)/(r-2)
If there is a solution better than that of (2,3,7), the following inequality must hold true:
1/2 + 1/q + 1/r
>
41/42
1/q + 1/r
>
10/21
21q + 21r
>
10qr
21q + 21r - 10qr
>
0
10qr - 21q - 21r
<
0
q(10r - 21) - 21r
<
0
q(10r - 21)
<
21r
q
<
(21r)/(10r-21)
So it is established that
(2r)/(r-2) < q < (21r)/(10r-21)
Now I will show there are no solutions that will match this inequality. Here are some individual cases:

r = 3: 6 < q < 7

r = 4: 4 < q < 4.421...

r = 5: 3.333... < q < 3.621...

r = 6: 3 < q < 3.231...

r = 7: 2.8 < q < 3 q > = 3 !

r = 8: 2.666... < q < 2.739 q > = 3 !

None of these inequalities has an integer solution. As r tends to infinity (2r)/(r-2) tends to 2 and (21r)/(10r-21) tends to 2.1. Therefore the upper bound will not exceed 3 for r > 8, so the inequality will continue to fail as q ³ 3.

Therefore the inequality (2r)/(r-2) < q < (21r)/(10r-21) has no integer solutions for q ³ 3, r ³ 3.

Therefore as shown earlier there is no case for p = 2 that yields a greater sum than the case (2,3,7).

So

p=2

q=3

r=7

Andrei's program(I haven't tested it!):

//fracmax

#include< iostream.h>

long double p,q,r,p1,q1,r1,max1;

void main() {

max1=0;

for(p=1;p< =20;p++) {

   for(q=1;q< =20;q++) {

      for(r=1;r< =20;r++) {

         if((1/p)+(1/q)+(1/r)< 1 && 1/p+1/q+1/r> max1) {

         max1=(1/p)+(1/q)+(1/r);p1=p;q1=q;r1=r;

         }

      }

   }

}

cout< < "p= « < p1< < "; q= « < q1< < "; r= « < r1< < "; maximum= « < max1;

}